Mono-and bis(trichlorostannyl) complexes [MCl(SnCl 3)(η 5-C 5 Me 5){P(OR) 3 }] (1, 2) and [M(SnCl... more Mono-and bis(trichlorostannyl) complexes [MCl(SnCl 3)(η 5-C 5 Me 5){P(OR) 3 }] (1, 2) and [M(SnCl 3) 2 (η 5-C 5 Me 5){P(OR) 3 }] (3, 4) (M = Rh, Ir; R = Me, Et) were prepared by allowing chloro compounds MCl 2 (η 5-C 5 Me 5)[P(OR) 3 ] to react with anhydrous SnCl 2 in refluxing 1,2-dichloroethane. Treatment of trichlorostannyl complexes of iridium 2 and 4 with NaBH 4 in ethanol afforded hydride-trihydridestannyl derivatives [IrH(SnH 3)(η 5-C 5 Me 5){P(OR) 3 }] (5) and bis(trihydridestannyl) [Ir(SnH 3) 2 (η 5-C 5 Me 5){P(OR) 3 }] (6), the reaction of which with methylpropiolate HC � CCOOMe led to trivinylstannyl derivatives [IrH{Sn[C (COOMe) = CH 2 ] 3 }(η 5-C 5 Me 5){P(OMe) 3 }] (7 a) and [Ir{Sn[CH=C(H) COOMe] 3 } 2 (η 5-C 5 Me 5){P(OMe) 3 }] (8 a). The complexes were characterised spectroscopically (IR and 1 H, 31 P, 13 C, 119 Sn NMR) and by X-ray crystal structure determination of [Ir(SnCl 3) 2 (η 5-C 5 Me 5) {P(OMe) 3 }] (4 a).
Dalton transactions (Cambridge, England : 2003), Jan 14, 2014
Iridanaphthalene complexes are synthesized from the corresponding methoxy(alkenyl)carbeneiridium ... more Iridanaphthalene complexes are synthesized from the corresponding methoxy(alkenyl)carbeneiridium compounds. The electronic character of the substituents on the 6-position of the metallanaphthalene ring is crucial from the point of view of the stability of the iridanaphthalene, [Ir[upper bond 1 start]Cp*{=C(OMe)CH=C(o-C[upper bond 1 end]6H4)(Ph)}(PMe3)]PF6, vs. its transformation to the corresponding indanone derivatives. Stability studies of the iridanaphthalene compounds revealed that strong electron donor substituents (-OMe) stabilize the iridanaphthalene, while weak electron donor (-Me) and electron withdrawing (-NO2) groups favor the formation of indanone derivatives. Two possible indanone isomers can be obtained in the conversion of the unstable iridanaphthalene complexes and a mechanism for the formation of these isomers is proposed.
Zeitschrift für anorganische und allgemeine Chemie, 2015
ABSTRACT Treatment of bis(cyanamide) [M(N≡CNEt2)2L4](BPh4)2 and bis(cyanoguanidine) [M{N≡CN(H)C(N... more ABSTRACT Treatment of bis(cyanamide) [M(N≡CNEt2)2L4](BPh4)2 and bis(cyanoguanidine) [M{N≡CN(H)C(NH2)=NH}2L4](BPh4)2 complexes [M = Fe, Ru, Os; L = P(OEt)3] with an excess of amine RNH2 (R = nPr, iPr) affords mixed-ligand complexes with cyanamide and amine [M(NH2R)(N≡CNEt2)L4](BPh4)2 (1a–5a) and [M(NH2R){N≡CN(H)C(NH2)=NH}L4](BPh4)2 (1b, 2b). The complexes were characterized by spectroscopy and X-ray crystal structure determination of [M(NH2iPr)(N≡CNEt2){P(OEt)3}4](BPh4)2 [M = Ru (3a), Os (5a)].
The mono- and binuclear hydride compounds fac-[ReH(CO)3L] (1a) and [{ReH(CO)4}2(μ-L)] (1b) have b... more The mono- and binuclear hydride compounds fac-[ReH(CO)3L] (1a) and [{ReH(CO)4}2(μ-L)] (1b) have been prepared by reaction of [ReH(CO)5] with Ph2PN(CH3)(CH2)2N(CH3)PPh2 (L) under UV light. Protonation reactions of the hydride compound 1a with equimolar amounts of HSO3CF3 or HCl yielded the triflato or the chlorido compounds fac-[Re(OSO2CF3)(CO)3L] (2) and fac-[ReCl(CO)3L] (3), respectively. The compounds have been characterised by elemental analysis, IR
Reaction of vinylidene complexes of Ru with hydrazines and hydroxylamines affords nitrile derivat... more Reaction of vinylidene complexes of Ru with hydrazines and hydroxylamines affords nitrile derivatives and amine or water. A reaction path based on 15N NMR studies and DFT calculations is proposed.
Zeitschrift für anorganische und allgemeine Chemie, 2003
Abstract The manganese carbonyl complex [MnBr (CO) 3 L](1), where L= Ph 2 POCH 2 CH 2 OPPh 2, was... more Abstract The manganese carbonyl complex [MnBr (CO) 3 L](1), where L= Ph 2 POCH 2 CH 2 OPPh 2, was prepared by reacting [MnBr (CO) 5] with the bidentate ligand 1, 2-Bis (diphenylphosphinite) ethane. From this compound and the appropriate phosphite, ...
ABSTRACT The first example of evolution of an iridanaphthalene into an indanone through an interm... more ABSTRACT The first example of evolution of an iridanaphthalene into an indanone through an intermediate indeniyl is reported, serving as a good example of starting material to obtain indanones. Two new iridanaphthalenes are obtained by intramolecular C−H activation of a phenyl ring of a carbene ligand in [IrCp*{C(OMe)CHCPh2}(L)]PF6 (L = PPh2Me, PMe3) complexes. It is demonstrated that these iridanaphthalene complexes can undergo a thermal reaction to give indeniyl complexes and 3-phenylindanone.
Trichlorogermyl complexes M(GeCl 3)(CO) n P 5À n (1e4) [M ¼ Mn, Re; n ¼ 2, 3; P ¼ PPh(OEt) 2 (a),... more Trichlorogermyl complexes M(GeCl 3)(CO) n P 5À n (1e4) [M ¼ Mn, Re; n ¼ 2, 3; P ¼ PPh(OEt) 2 (a), P(OEt) 3 (b)] were prepared by allowing chloro compounds MCl(CO) n P 5À n to react with an excess of GeCl 2 dioxane in 1,2-dichloroethane. Treatment of compounds 1e4 with LiAlH 4 in thf yielded trihydridegermyl derivatives M(GeH 3)(CO) n P 5Àn (5e8), whereas treatment of the same complexes with NaBH 4 in ethanol afforded triethoxygermyl derivatives M[Ge(OEt) 3 ](CO) n P 5Àn (9e11). Trimethylgermyl compounds M(GeMe 3)(CO) n P 5Àn (12, 13) and the alkynylgermyl derivative Mn[Ge(C^CPh) 3 ](CO) 3 [P-Ph(OEt) 2 ] 2 (14a) were also prepared by allowing trichlorogermyl compounds 1e4 to react with either MgBrMe or Li þ C^CPh À , respectively, in thf. Treatment of compound Re(GeCl 3)(CO) 3 [PPh(OEt) 2 ] 2 (4a) with SnCl 2 2H 2 O gave the stannyl-germyl derivative Re[GeCl 2 (SnCl 3)](CO) 3 [PPh(OEt) 2 ] 2 (15a). The complexes were characterised by spectroscopy and X-ray crystal structure determination of 4a, 5a, and 13a.
Hydrazine complexes [MCl(h 6-p-cymene)(RNHNH 2)L]BPh 4 (1e6) [M ¼ Ru, Os; R ¼ H, Me, Ph; L ¼ P(OE... more Hydrazine complexes [MCl(h 6-p-cymene)(RNHNH 2)L]BPh 4 (1e6) [M ¼ Ru, Os; R ¼ H, Me, Ph; L ¼ P(OEt) 3 , PPh(OEt) 2 , PPh 2 OEt] were prepared by allowing dichloro complexes MCl 2 (h 6-p-cymene)L to react with hydrazines RNHNH 2 in the presence of NaBPh 4. Treatment of ruthenium complexes [RuCl(h 6p-cymene)(RNHNH 2)L]BPh 4 with Pb(OAc) 4 led to acetate complex [Ru(k 2 eO 2 CCH 3)(h 6-p-cymene)L]BPh 4 (7). Instead, the reaction of osmium derivatives [OsCl(h 6-p-cymene)(CH 3 NHNH 2)L]BPh 4 with Pb(OAc) 4 afforded the methyldiazenido complex [Os(CH 3 N 2)(h 6-p-cymene)L}]BPh 4 (8). Treatment with HCl of this diazenido complex 8 led to the methyldiazene cation [OsCl(CH 3 N]NH)(h 6-p-cymene)L}] þ (9 þ). The complexes were characterised spectroscopically and by X-ray crystal structure determination of [OsCl(h 6-p-cymene)(PhNHNH 2){PPh(OEt) 2 }]BPh 4 (6b) and [Ru(k 2 eO 2 CCH 3)(h 6-p-cymene){PPh(OEt) 2 }] BPh 4 (7b).
The dicarbonylhydride complex cis,mer-[ReH(CO)2{PPh(OMe)2}3] (1) was serendipitously obtained whe... more The dicarbonylhydride complex cis,mer-[ReH(CO)2{PPh(OMe)2}3] (1) was serendipitously obtained when, in an attempt to replace a CO ligand by the phosphonite ligand PPh(OMe)2 in [ReH(CO)3(L)] (L=PPh2OCH2CH2OPPh2), this complex was treated with PPh(OMe)2 under UV irradiation. The complex 1 was characterized by IR, 1H and 31P{1H} NMR spectroscopy and by crystal structure determination. The spectroscopic features are consequent with the cis,mer configuration
The solid state structures of the compounds GaI3•PPh3 and Ga2I6•dppe ( dppe = 1,2-bis(diphenylpho... more The solid state structures of the compounds GaI3•PPh3 and Ga2I6•dppe ( dppe = 1,2-bis(diphenylphosphino)ethane ) have been determined. For the former, in which the GaI3P core has C3v symmetry, the structure is trigonal, with a = 14.961(2) Å, c = 16.509(3) Å, V = 3199.5(4) Å3, Z = 6, space group [Formula: see text]. In Ga2I6•dppe, the ligand bridges two GaI3P centres; the structure is monoclinic, a = 10.196(7) Å, b = 15.363(1) Å, c = 23.027(9) Å, β = 98.735(4)°, V = 3565.1(3.2) Å3Z = 4, space group P21/n The use of 31P NMR spectroscopy shows that GaI3•PPh3 is slightly dissociated in nonaqueous solution, and the effect of adding Ph3P or I− has been investigated. Similar studies with Ga2I6•dppe are also reported. In each system, four-coordination at gallium is dominant; an equally important factor is the dimerization of uncomplexed GaI3 to Ga2I6 in these solutions. Keywords: gallium(III) iodide, complexes, phosphorus, NMR, crystallography.
p-tolyl; Ar1Ar2 = C 12 H 8) were prepared following the method previously reported. 1,2 All solve... more p-tolyl; Ar1Ar2 = C 12 H 8) were prepared following the method previously reported. 1,2 All solvents were dried over appropriate drying agents, degased on a vacuum line, and distilled into vacuum-tight storage flasks. RuCl 3 •3H 2 O was a Pressure Chemical Co. (USA) product; other reagents were purchased from commercial sources in the highest available purity and used as received. Infrared spectra were recorded on a Perkin-Elmer Spectrum-One FT-IR spectrophotometer. NMR spectra (1 H, 13 C, 31 P) were obtained on an AVANCE 300 Bruker spectrometer at temperatures between-90 and +30 °C, unless otherwise noted. 1 H and 13 C spectra are referred to internal tetramethylsilane. 31 P{ 1 H} chemical shifts are reported with respect to 85% H 3 PO 4 , with downfield shifts considered positive. COSY, HMQC and HMBC NMR experiments were performed with standard programs. The iNMR software package 3 was used to treat NMR data. Melting points (mp) were determined in capillary on a Büchi 535 apparatus. The conductivity of 10-3 mol dm-3 solutions of the complexes in CH 3 NO 2 at 25 °C was measured on a Radiometer CDM 83. Elemental analyses were determined in the Microanalytical Laboratory of the
Zeitschrift für anorganische und allgemeine Chemie, 2019
Imine complexes [IrCl(η 5-C 5 Me 5){κ 1-NH=C(H)Ar}{P(OR) 3 }]BPh 4 (1, 2) (Ar = C 6 H 5 , 4-CH 3 ... more Imine complexes [IrCl(η 5-C 5 Me 5){κ 1-NH=C(H)Ar}{P(OR) 3 }]BPh 4 (1, 2) (Ar = C 6 H 5 , 4-CH 3 C 6 H 4 ; R = Me, Et) were prepared by allowing chloro complexes [IrCl 2 (η 5-C 5 Me 5){P(OR) 3 }] to react with benzyl azides ArCH 2 N 3. Bis(imine) complexes [Ir(η 5-C 5 Me 5){κ 1-NH=C(H)Ar} 2 {P(OR) 3 }](BPh 4) 2 (3, 4) were also prepared by reacting [IrCl 2 (η 5-C 5 Me 5){P(OR) 3 }] first with AgOTf and then with benzyl azide. Depending on the experimental conditions, treatment of the dinuclear complex [IrCl 2 (η 5-C 5 Me 5)] 2 with benzyl
has been the object of several papers from our laboratory. Starting from the metal as the anode o... more has been the object of several papers from our laboratory. Starting from the metal as the anode of an electrolytic cell, the synthesis of metal-pyrrolaldiminates has been described (Castro, Romero, Garcia-Vfizquez, Durfin, Sousa, Castellano & Zukerman-Schpector, 1992). We have now applied the same method to the synthesis of the complex dichloro[5,8-dimethyl-1,12-di-2-pyrrolyl)-2,5,8,1 ltetraaza-1,11-dodecadiene]cadmium(I I) (I), and determined its structure by X-ray diffraction.
The rhenium complex fac-[ReOCl3L][1; L= 1, 3-bis (diphenylphosphanyloxy) propane] was prepared by... more The rhenium complex fac-[ReOCl3L][1; L= 1, 3-bis (diphenylphosphanyloxy) propane] was prepared by reacting L with [ReOCl3 (AsPh3) 2]. Refluxing complex 1 in ethanol gave [ReOCl2 (OEt) L](2), which X-ray crystallography showed to have an octahedral rhenium ...
The electrochemical oxidation of anodic cobalt in acetonitrile solutions of [(4-methylphenyl)sulf... more The electrochemical oxidation of anodic cobalt in acetonitrile solutions of [(4-methylphenyl)sulfonyl]-1H-imino-2-phenyl-2-oxazoline ligands, [HTs ROz], affords compounds of general formula [Co(Ts ROz) 2 ]. All complexes have been characterised by microanalysis, IR and UV-Vis spectroscopy, magnetic measurements and, in the cases of HTs 4 i PrOz, [Co(Ts Oz) 2 ], [Co(Ts 4MeOz) 2 ], [Co(Ts 4 i PrOz) 2 ] and [Co(Ts 4EtOz) 2 ], by single-crystal X-ray diffraction.
Mono-and bis(trichlorostannyl) complexes [MCl(SnCl 3)(η 5-C 5 Me 5){P(OR) 3 }] (1, 2) and [M(SnCl... more Mono-and bis(trichlorostannyl) complexes [MCl(SnCl 3)(η 5-C 5 Me 5){P(OR) 3 }] (1, 2) and [M(SnCl 3) 2 (η 5-C 5 Me 5){P(OR) 3 }] (3, 4) (M = Rh, Ir; R = Me, Et) were prepared by allowing chloro compounds MCl 2 (η 5-C 5 Me 5)[P(OR) 3 ] to react with anhydrous SnCl 2 in refluxing 1,2-dichloroethane. Treatment of trichlorostannyl complexes of iridium 2 and 4 with NaBH 4 in ethanol afforded hydride-trihydridestannyl derivatives [IrH(SnH 3)(η 5-C 5 Me 5){P(OR) 3 }] (5) and bis(trihydridestannyl) [Ir(SnH 3) 2 (η 5-C 5 Me 5){P(OR) 3 }] (6), the reaction of which with methylpropiolate HC � CCOOMe led to trivinylstannyl derivatives [IrH{Sn[C (COOMe) = CH 2 ] 3 }(η 5-C 5 Me 5){P(OMe) 3 }] (7 a) and [Ir{Sn[CH=C(H) COOMe] 3 } 2 (η 5-C 5 Me 5){P(OMe) 3 }] (8 a). The complexes were characterised spectroscopically (IR and 1 H, 31 P, 13 C, 119 Sn NMR) and by X-ray crystal structure determination of [Ir(SnCl 3) 2 (η 5-C 5 Me 5) {P(OMe) 3 }] (4 a).
Dalton transactions (Cambridge, England : 2003), Jan 14, 2014
Iridanaphthalene complexes are synthesized from the corresponding methoxy(alkenyl)carbeneiridium ... more Iridanaphthalene complexes are synthesized from the corresponding methoxy(alkenyl)carbeneiridium compounds. The electronic character of the substituents on the 6-position of the metallanaphthalene ring is crucial from the point of view of the stability of the iridanaphthalene, [Ir[upper bond 1 start]Cp*{=C(OMe)CH=C(o-C[upper bond 1 end]6H4)(Ph)}(PMe3)]PF6, vs. its transformation to the corresponding indanone derivatives. Stability studies of the iridanaphthalene compounds revealed that strong electron donor substituents (-OMe) stabilize the iridanaphthalene, while weak electron donor (-Me) and electron withdrawing (-NO2) groups favor the formation of indanone derivatives. Two possible indanone isomers can be obtained in the conversion of the unstable iridanaphthalene complexes and a mechanism for the formation of these isomers is proposed.
Zeitschrift für anorganische und allgemeine Chemie, 2015
ABSTRACT Treatment of bis(cyanamide) [M(N≡CNEt2)2L4](BPh4)2 and bis(cyanoguanidine) [M{N≡CN(H)C(N... more ABSTRACT Treatment of bis(cyanamide) [M(N≡CNEt2)2L4](BPh4)2 and bis(cyanoguanidine) [M{N≡CN(H)C(NH2)=NH}2L4](BPh4)2 complexes [M = Fe, Ru, Os; L = P(OEt)3] with an excess of amine RNH2 (R = nPr, iPr) affords mixed-ligand complexes with cyanamide and amine [M(NH2R)(N≡CNEt2)L4](BPh4)2 (1a–5a) and [M(NH2R){N≡CN(H)C(NH2)=NH}L4](BPh4)2 (1b, 2b). The complexes were characterized by spectroscopy and X-ray crystal structure determination of [M(NH2iPr)(N≡CNEt2){P(OEt)3}4](BPh4)2 [M = Ru (3a), Os (5a)].
The mono- and binuclear hydride compounds fac-[ReH(CO)3L] (1a) and [{ReH(CO)4}2(μ-L)] (1b) have b... more The mono- and binuclear hydride compounds fac-[ReH(CO)3L] (1a) and [{ReH(CO)4}2(μ-L)] (1b) have been prepared by reaction of [ReH(CO)5] with Ph2PN(CH3)(CH2)2N(CH3)PPh2 (L) under UV light. Protonation reactions of the hydride compound 1a with equimolar amounts of HSO3CF3 or HCl yielded the triflato or the chlorido compounds fac-[Re(OSO2CF3)(CO)3L] (2) and fac-[ReCl(CO)3L] (3), respectively. The compounds have been characterised by elemental analysis, IR
Reaction of vinylidene complexes of Ru with hydrazines and hydroxylamines affords nitrile derivat... more Reaction of vinylidene complexes of Ru with hydrazines and hydroxylamines affords nitrile derivatives and amine or water. A reaction path based on 15N NMR studies and DFT calculations is proposed.
Zeitschrift für anorganische und allgemeine Chemie, 2003
Abstract The manganese carbonyl complex [MnBr (CO) 3 L](1), where L= Ph 2 POCH 2 CH 2 OPPh 2, was... more Abstract The manganese carbonyl complex [MnBr (CO) 3 L](1), where L= Ph 2 POCH 2 CH 2 OPPh 2, was prepared by reacting [MnBr (CO) 5] with the bidentate ligand 1, 2-Bis (diphenylphosphinite) ethane. From this compound and the appropriate phosphite, ...
ABSTRACT The first example of evolution of an iridanaphthalene into an indanone through an interm... more ABSTRACT The first example of evolution of an iridanaphthalene into an indanone through an intermediate indeniyl is reported, serving as a good example of starting material to obtain indanones. Two new iridanaphthalenes are obtained by intramolecular C−H activation of a phenyl ring of a carbene ligand in [IrCp*{C(OMe)CHCPh2}(L)]PF6 (L = PPh2Me, PMe3) complexes. It is demonstrated that these iridanaphthalene complexes can undergo a thermal reaction to give indeniyl complexes and 3-phenylindanone.
Trichlorogermyl complexes M(GeCl 3)(CO) n P 5À n (1e4) [M ¼ Mn, Re; n ¼ 2, 3; P ¼ PPh(OEt) 2 (a),... more Trichlorogermyl complexes M(GeCl 3)(CO) n P 5À n (1e4) [M ¼ Mn, Re; n ¼ 2, 3; P ¼ PPh(OEt) 2 (a), P(OEt) 3 (b)] were prepared by allowing chloro compounds MCl(CO) n P 5À n to react with an excess of GeCl 2 dioxane in 1,2-dichloroethane. Treatment of compounds 1e4 with LiAlH 4 in thf yielded trihydridegermyl derivatives M(GeH 3)(CO) n P 5Àn (5e8), whereas treatment of the same complexes with NaBH 4 in ethanol afforded triethoxygermyl derivatives M[Ge(OEt) 3 ](CO) n P 5Àn (9e11). Trimethylgermyl compounds M(GeMe 3)(CO) n P 5Àn (12, 13) and the alkynylgermyl derivative Mn[Ge(C^CPh) 3 ](CO) 3 [P-Ph(OEt) 2 ] 2 (14a) were also prepared by allowing trichlorogermyl compounds 1e4 to react with either MgBrMe or Li þ C^CPh À , respectively, in thf. Treatment of compound Re(GeCl 3)(CO) 3 [PPh(OEt) 2 ] 2 (4a) with SnCl 2 2H 2 O gave the stannyl-germyl derivative Re[GeCl 2 (SnCl 3)](CO) 3 [PPh(OEt) 2 ] 2 (15a). The complexes were characterised by spectroscopy and X-ray crystal structure determination of 4a, 5a, and 13a.
Hydrazine complexes [MCl(h 6-p-cymene)(RNHNH 2)L]BPh 4 (1e6) [M ¼ Ru, Os; R ¼ H, Me, Ph; L ¼ P(OE... more Hydrazine complexes [MCl(h 6-p-cymene)(RNHNH 2)L]BPh 4 (1e6) [M ¼ Ru, Os; R ¼ H, Me, Ph; L ¼ P(OEt) 3 , PPh(OEt) 2 , PPh 2 OEt] were prepared by allowing dichloro complexes MCl 2 (h 6-p-cymene)L to react with hydrazines RNHNH 2 in the presence of NaBPh 4. Treatment of ruthenium complexes [RuCl(h 6p-cymene)(RNHNH 2)L]BPh 4 with Pb(OAc) 4 led to acetate complex [Ru(k 2 eO 2 CCH 3)(h 6-p-cymene)L]BPh 4 (7). Instead, the reaction of osmium derivatives [OsCl(h 6-p-cymene)(CH 3 NHNH 2)L]BPh 4 with Pb(OAc) 4 afforded the methyldiazenido complex [Os(CH 3 N 2)(h 6-p-cymene)L}]BPh 4 (8). Treatment with HCl of this diazenido complex 8 led to the methyldiazene cation [OsCl(CH 3 N]NH)(h 6-p-cymene)L}] þ (9 þ). The complexes were characterised spectroscopically and by X-ray crystal structure determination of [OsCl(h 6-p-cymene)(PhNHNH 2){PPh(OEt) 2 }]BPh 4 (6b) and [Ru(k 2 eO 2 CCH 3)(h 6-p-cymene){PPh(OEt) 2 }] BPh 4 (7b).
The dicarbonylhydride complex cis,mer-[ReH(CO)2{PPh(OMe)2}3] (1) was serendipitously obtained whe... more The dicarbonylhydride complex cis,mer-[ReH(CO)2{PPh(OMe)2}3] (1) was serendipitously obtained when, in an attempt to replace a CO ligand by the phosphonite ligand PPh(OMe)2 in [ReH(CO)3(L)] (L=PPh2OCH2CH2OPPh2), this complex was treated with PPh(OMe)2 under UV irradiation. The complex 1 was characterized by IR, 1H and 31P{1H} NMR spectroscopy and by crystal structure determination. The spectroscopic features are consequent with the cis,mer configuration
The solid state structures of the compounds GaI3•PPh3 and Ga2I6•dppe ( dppe = 1,2-bis(diphenylpho... more The solid state structures of the compounds GaI3•PPh3 and Ga2I6•dppe ( dppe = 1,2-bis(diphenylphosphino)ethane ) have been determined. For the former, in which the GaI3P core has C3v symmetry, the structure is trigonal, with a = 14.961(2) Å, c = 16.509(3) Å, V = 3199.5(4) Å3, Z = 6, space group [Formula: see text]. In Ga2I6•dppe, the ligand bridges two GaI3P centres; the structure is monoclinic, a = 10.196(7) Å, b = 15.363(1) Å, c = 23.027(9) Å, β = 98.735(4)°, V = 3565.1(3.2) Å3Z = 4, space group P21/n The use of 31P NMR spectroscopy shows that GaI3•PPh3 is slightly dissociated in nonaqueous solution, and the effect of adding Ph3P or I− has been investigated. Similar studies with Ga2I6•dppe are also reported. In each system, four-coordination at gallium is dominant; an equally important factor is the dimerization of uncomplexed GaI3 to Ga2I6 in these solutions. Keywords: gallium(III) iodide, complexes, phosphorus, NMR, crystallography.
p-tolyl; Ar1Ar2 = C 12 H 8) were prepared following the method previously reported. 1,2 All solve... more p-tolyl; Ar1Ar2 = C 12 H 8) were prepared following the method previously reported. 1,2 All solvents were dried over appropriate drying agents, degased on a vacuum line, and distilled into vacuum-tight storage flasks. RuCl 3 •3H 2 O was a Pressure Chemical Co. (USA) product; other reagents were purchased from commercial sources in the highest available purity and used as received. Infrared spectra were recorded on a Perkin-Elmer Spectrum-One FT-IR spectrophotometer. NMR spectra (1 H, 13 C, 31 P) were obtained on an AVANCE 300 Bruker spectrometer at temperatures between-90 and +30 °C, unless otherwise noted. 1 H and 13 C spectra are referred to internal tetramethylsilane. 31 P{ 1 H} chemical shifts are reported with respect to 85% H 3 PO 4 , with downfield shifts considered positive. COSY, HMQC and HMBC NMR experiments were performed with standard programs. The iNMR software package 3 was used to treat NMR data. Melting points (mp) were determined in capillary on a Büchi 535 apparatus. The conductivity of 10-3 mol dm-3 solutions of the complexes in CH 3 NO 2 at 25 °C was measured on a Radiometer CDM 83. Elemental analyses were determined in the Microanalytical Laboratory of the
Zeitschrift für anorganische und allgemeine Chemie, 2019
Imine complexes [IrCl(η 5-C 5 Me 5){κ 1-NH=C(H)Ar}{P(OR) 3 }]BPh 4 (1, 2) (Ar = C 6 H 5 , 4-CH 3 ... more Imine complexes [IrCl(η 5-C 5 Me 5){κ 1-NH=C(H)Ar}{P(OR) 3 }]BPh 4 (1, 2) (Ar = C 6 H 5 , 4-CH 3 C 6 H 4 ; R = Me, Et) were prepared by allowing chloro complexes [IrCl 2 (η 5-C 5 Me 5){P(OR) 3 }] to react with benzyl azides ArCH 2 N 3. Bis(imine) complexes [Ir(η 5-C 5 Me 5){κ 1-NH=C(H)Ar} 2 {P(OR) 3 }](BPh 4) 2 (3, 4) were also prepared by reacting [IrCl 2 (η 5-C 5 Me 5){P(OR) 3 }] first with AgOTf and then with benzyl azide. Depending on the experimental conditions, treatment of the dinuclear complex [IrCl 2 (η 5-C 5 Me 5)] 2 with benzyl
has been the object of several papers from our laboratory. Starting from the metal as the anode o... more has been the object of several papers from our laboratory. Starting from the metal as the anode of an electrolytic cell, the synthesis of metal-pyrrolaldiminates has been described (Castro, Romero, Garcia-Vfizquez, Durfin, Sousa, Castellano & Zukerman-Schpector, 1992). We have now applied the same method to the synthesis of the complex dichloro[5,8-dimethyl-1,12-di-2-pyrrolyl)-2,5,8,1 ltetraaza-1,11-dodecadiene]cadmium(I I) (I), and determined its structure by X-ray diffraction.
The rhenium complex fac-[ReOCl3L][1; L= 1, 3-bis (diphenylphosphanyloxy) propane] was prepared by... more The rhenium complex fac-[ReOCl3L][1; L= 1, 3-bis (diphenylphosphanyloxy) propane] was prepared by reacting L with [ReOCl3 (AsPh3) 2]. Refluxing complex 1 in ethanol gave [ReOCl2 (OEt) L](2), which X-ray crystallography showed to have an octahedral rhenium ...
The electrochemical oxidation of anodic cobalt in acetonitrile solutions of [(4-methylphenyl)sulf... more The electrochemical oxidation of anodic cobalt in acetonitrile solutions of [(4-methylphenyl)sulfonyl]-1H-imino-2-phenyl-2-oxazoline ligands, [HTs ROz], affords compounds of general formula [Co(Ts ROz) 2 ]. All complexes have been characterised by microanalysis, IR and UV-Vis spectroscopy, magnetic measurements and, in the cases of HTs 4 i PrOz, [Co(Ts Oz) 2 ], [Co(Ts 4MeOz) 2 ], [Co(Ts 4 i PrOz) 2 ] and [Co(Ts 4EtOz) 2 ], by single-crystal X-ray diffraction.
Arylaldazine and acetoneazine complexes [IrCl([small eta]5-C5Me5){[small kappa]1-[N[double bond{,... more Arylaldazine and acetoneazine complexes [IrCl([small eta]5-C5Me5){[small kappa]1-[N[double bond{,} length as m-dash]C(H)(R2C6H4)]-N[double bond{,} length as m-dash]C(H)(R2C6H4)}{P(OR1)3}]BPh4 (1{,} 2) and [IrCl([small eta]5-C5Me5){[small kappa]1-[N[double bond{,} length as m-dash]C(CH3)2]-N[double bond{,} length as m-dash]C(CH3)2}{P(OR1)3}]BPh4 (3{,} 4) [R1 = Me (1{,} 3){,} Et (2{,} 4); R2 = H (a){,} 4-CH3 (b){,} 2{,}6-(CH3)2 (f)] were prepared by allowing chloro complexes IrCl2([small eta]5-C5Me5)[P(OR1)3] to react first with AgOTf and then with the appropriate azine. In solution{,} [small kappa]1-complexes 1-4 undergo a metalation reaction{,} affording chelate [small kappa]2-azine derivatives [Ir[upper bond 1 end]{[small kappa]2-R2C6H3(H)C[double bond{,} length as m-dash]N[lower bond 1 start]-N[double bond{,} length as m-dash]C(H)(R2C6H4)}([small eta]5-C5Me5){P(OR1)3}]BPh4 (5{,} 6) and [Ir[upper bond 1 start]{[small kappa]2-CH2(CH3)C[double bond{,} length as m-dash]N[lower bond 1 start]-N[double bond{,} length as m-dash]C(CH3)2}([small eta]5-C5Me5){P(OR1)3}]BPh4 (7{,} 8) [R1 = Me (5{,} 7){,} Et (6{,} 8); R2 = H (a){,} 4-CH3 (b){,} 4-CH3O (c); 4-F (d){,} 4-NO2 (e)]. The complexes were characterised spectroscopically and by X-ray crystal structure determination of [Ir[upper bond 1 end]{[small kappa]2-C6H4(H)C[double bond{,} length as m-dash]N[lower bond 1 start]-N[double bond{,} length as m-dash]C(H)(C6H5)}([small eta]5-C5Me5){P(OEt)3}]BPh4 (6a). Most of the [small kappa]2-arylazine derivatives showed photoluminescence properties upon excitation with near-UV and violet light{,} with emission peaks at around 650 nm. The photoluminescence features were rationalised according to DFT calculations.
Diazoalkane complexes [Ru(Tp)(N2CAr1Ar2)(PPh3)L]BPh4 (1 and 2) [Tp = tris(pyrazolyl)borate; L = P... more Diazoalkane complexes [Ru(Tp)(N2CAr1Ar2)(PPh3)L]BPh4 (1 and 2) [Tp = tris(pyrazolyl)borate; L = P(OMe)3{,} P(OEt)3; Ar1 = Ar2 = Ph; Ar1 = Ph{,} Ar2 = p-tolyl; Ar1Ar2 = C12H8] were prepared by allowing chloro-compounds RuCl(Tp)(PPh3)L to react with diazoalkane in the presence of NaBPh4. Acrylonitrile CH2[double bond{,} length as m-dash]C(H)CN reacts with diazoalkane complexes to give 3H-pyrazole derivatives [Ru(Tp){N[double bond{,} length as m-dash]NC(Ar1Ar2)CH(CN)CH2}(PPh3){P(OMe)3}]BPh4 and [Ru(Tp){N[double bond{,} length as m-dash]NC(Ar1Ar2)CH2C(H)CN}(PPh3){P(OMe)3}]BPh4 (3). Diazoalkane complexes [Ru(bpza)(N2CAr1Ar2)(PPh3)2]BPh4 (4) [bpza = bis(pyrazolyl)acetate] were also prepared. All complexes were characterised by IR and NMR spectroscopy and X-ray crystal structure determination of [Ru(Tp){N2C(Ph)(p-tolyl)}(PPh3){P(OMe)3}]BPh4 (1b). The differences exhibited by [Ru(Tp){N2C(Ph)(p-tolyl)}(PPh3){P(OMe)3}]+ and [Ru(Cp){N2C(Ph)(p-tolyl)}(PPh3){P(OMe)3}]+{,} as regards coordination of the diazoalkane ligand and reactivity towards alkenes{,} were explained on the basis of a comparative DFT study.
The diketone-based oxo-vanadium(V) dimer complex has been synthesized and characterized.Crystal s... more The diketone-based oxo-vanadium(V) dimer complex has been synthesized and characterized.Crystal structures of ligand and its complex have been determined by single crystal X-ray diffraction analysis.The complex is six coordinated, in which V(V) complex has a distorted octahedral geometry.The antimicrobial activities of the synthesized compounds were investigated experimentally and theoretically.A diketone-based tridentate Schiff base, 3-[(2-hydroxyphenyl)amino]-1,3-diphenylprop-2-en-1-one (H2L), and its oxo-vanadium(V) dimer complex, [VO(L)(OMe)]2, were synthesized and characterized using spectroscopic and physicochemical techniques. Single crystal X-ray diffraction indicated that the Schiff base ligand in its deprotonated form was found to bind to the V(V) ion through the azomethine nitrogen, amine and phenolic oxygens in a distorted octahedral geometry. The other positions around the V(V) center were occupied by an oxido group and two oxygens from methoxido ligands. Antimicrobial studies showed that the synthesized complex indicated significant antimicrobial activities against Escherichia coli (ATCC 25922) and Staphylococcus aureus (ATCC 33591 and 29213) bacteria while no antibacterial activity was observed for the ligand alone. The potential of [VO(L)(OMe)]2 as an antimicrobial agent, was additionally investigated using molecular docking of the complex with GlcN-6-P synthase.
Abstract A tridentate \{ONO\} ligand (E)-N′-((2-hydroxynaphthalen-1-yl)methylene)acetohydrazide [... more Abstract A tridentate \{ONO\} ligand (E)-N′-((2-hydroxynaphthalen-1-yl)methylene)acetohydrazide [HL] and its cationic Cu(II) complex [Cu(L)(H2O)]NO3 were synthesized and characterized by means of elemental analysis, FT-IR and UV–Vis spectrometry and conductivity measurements. The structure of the complex was determined using single crystal X-ray diffraction. The obtained data revealed that the Cu(II) center is coordinated by two oxygens and one nitrogen of the ligand. The fourth position is occupied by oxygen atom of a coordinated water molecule. X-ray data obtained showed that this complex possessed distorted square planar geometry around Cu(II) ion. Nitrate anion as the counter ion occupied the second sphere around the Cu(II) center via hydrogen bonding. The electrochemical behavior of the free ligand and its Cu(II) complex were studied using cyclic voltammetry. Nanoparticles (NPs) of CuO with the average size of 23 nm were prepared with thermal decomposition of the title complex and then were characterized using X-ray powder diffraction (XRD). Anti-cancer activities of the title compounds against human breast cancer (MCF-7 cells viability) were investigated and compared with each other. It was found that [Cu(L)(H2O)]NO3 complex showed higher anticancer activity than the others.
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Papers by Jesús Castro