Daphne Boys

Bis(diphenylphosphino)methane and its sulphide or selenide derivatives as ligands in ruthenium(II) and rhodium(III) complexes: Crystal structure of [(η6C6Me6)Ru{η3(SPPh2)2CH}]ClO4

Abstract Reaction of complexes [( η 6 C 6 Me 6 )RuCl 2 ] 2 and [( η 5 C 5 Me 5 )RhCl 2 ] 2 with the ligands L  Ph 2 PCH 2 PPh 2 (dppm) or Ph 2 PCH 2 P(Se)Ph 2 in benzene solutions led to neutral complexes with the general formula [(ring)MCl 2 ( η 1 L)]. The reactivity of the uncoordinated P atom of dppm has been studied. When the reaction was carried out in methanol solutions, cationic complexes, with the ligands acting in their bidentate form, were obtained. Similar cationic perchlorate complexes were prepared using acetone as solvent in the presence of sodium perchlorate, yielding [(ring)MCl( η 2 L)ClO 4 , where L  Ph 2 PCH 2 PPh 2 , Ph 2 PCH 2 P(Se)Ph 2 or Ph 2 P(S)CH 2 P(S)Ph 2 . The complex [( η 6 C 6 Me 6 )RuCl{ η 2 (SPPh) 2 CH 2 -S,S′}]ClO 4 reacted with sodium hydride in tetrahydrofuran or thallium pyrazolate in dichloromethane solution by deprotonation of the coordinated bidentate ligand giving the complex [( η 6 C 6 Me 6 )Ru{ η 3 (SPPh 2 ) 2 CH-C,S,S′}]ClO 4 . The structure of this compl has been determined by single crystal X-ray diffraction methods. The complex contains a tridentate C,S,S′-bonded ligand occupying three coordination positions of a distorted octahedral ruthenium centre, with an η 6 C 6 Me 6 group completing the coordination sphere.

Synthesis, characterization and crystal structure of [Ru(tppz)(4,4′-(CH3)2bpy)Cl](PF6), (tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine)

Abstract The synthesis and characterization of the complex [Ru(tppz)(4,4′-(CH 3 ) 2 bpy)Cl] + , where tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine, is reported. The ion was obtained in a one pot synthesis by reduction of Ru(4,4′-(CH 3 ) 2 bpy)Cl 4 with triethylamine in the presence of tppz, and isolated as the hexafluorophosphate salt. The structure of [Ru(tppz)(4,4′-(CH 3 ) 2 bpy)Cl](PF 6 ), 1 , was established by X-ray diffraction. The ruthenium atom is in a highly distorted octahedral environment with the 4,4′-(CH 3 ) 2 bpy nitrogens, the pyrazine central nitrogen of tppz, and chlorine defining the best mean equatorial plane. The axial positions are occupied by the nitrogens of the coordinated pyridyl rings of tppz. The Ru—N(tppz) bond to the central ring is short [1.962(9) A], while the Ru—N(4,4′(CH 3 ) 2 bpy) bond trans to it is lengthened towards a single bond distance [2.096(10) A]. This enhances the distortion in coordination of the octahedron, mainly produced by the bite angle of tppz. The distortions in 1 are evident in the 1 H-NMR spectra by the shifts of characteristic resonances upfield and downfield relative to the ligand.

New coordination mode of bis(diphenylphosphine) methanide diselenide. Synthesis and X-ray crystal structure of [(η5 C5Me5)Rh{η3 (SePPh2)2CH&}]ClO4

Abstract The dinuclear complexes [(η5 C5Me5)RhCl2]2 and [(η6 C6Me6)RuCl2]2 reacted with dppmSe2 giving the cationic compounds [(η5 C5Me5)RhCl{η2 (SePPh2)2CH2&}]+ (1) and [(η6 C6Me6)RuCl{η2 (SePPh2)2CH2&}]+ (2), which were isolated as perchlorate salts. Deprotonation reactions of these compounds yielded the new complexes [(η5 C5Me5)Rh{η3 (SePPh2)2CH&}]ClO4 (3) and [(η6 C6Me6)Ru{η3 (SePPh2)2CH&}]ClO4 (4), respectively, in which the anionic methanide diselenide ligand is acting as a tripod ligand, with a C,Se,Se′-donor set. The structure of3 has been determined by X-ray crystallography.

Organometallic iron (II) hydrazines and hydrazones — syntheses, characterisations and the X-ray crystal structures of [Fe(η5-Cp)(η6-C6H5NHNH2)]+PF6− and [Fe(η5-Cp)(η6-p-MeC6H4NHNCMe2)]+PF6−

The three new organometallic hydrazines [Fe(η 5 -Cp)(η 6 -RC 6 H 4 NHNH 2 )] + PF 6 − , CpC 5 H 5 , RH, [ 1 ] + PF 6 − ; m -Me, [ 2 ] + PF 6 − ; p -MeO, [ 3 ] + PF 6 − , were synthesised and characterised. They were obtained in CH 2 Cl 2 by reaction of the hydrazine monohydrate, NH 2 NH 2 ·H 2 O, with the corresponding precursors [Fe(η 5 -Cp)(η 6 -RC 6 H 4 Cl)] + PF 6 − . Similarly to free conventional organic hydrazines, the organometallic hydrazines [ 1 ] + PF 6 − and [ 3 ] + PF 6 − react with acetone affording hydrazones formulated as [Fe(η 5 -Cp)(η 6 -RC 6 H 4 NHNCMe 2 )] + PF 6 − , RH, [ 6 ] + PF 6 − ; p -MeO, [ 7 ] + PF 6 − . Likewise, the two other organometallic hydrazones containing the substituent groups R o -Cl, [ 8 ] + PF 6 − and p -Me, [ 9 ] + PF 6 − were also obtained from their parent hydrazine precursors [ 4 ] + PF 6 − and [ 5 ] + PF 6 − , respectively. All the new compounds were characterised by elemental analysis and IR, UV–vis, 1 H- and 13 C-NMR spectroscopy. The crystalline and molecular structures of [ 1 ] + PF 6 − and [ 9 ] + PF 6 − were determined by single crystal X-ray crystallographic analysis. Both structures show a cyclohexadienyl-like character at the coordinated C 6 ring of the phenylhydrazine and the p -methylphenylhydrazone with a folding angle of 6.0(5) and 7.1(6)°, respectively.

Synthesis and characterization of heterodinuclear RuPt and IrPt complexes containing pyrazolate bridging ligands. Crystal structure of [(η5-C5Me5)Ir(μ-pz)3PtMe3] (pz=pyrazolate)

The reaction of the metallo–ligand [Ru(η 6 - p -cymene)(pz) 2 (Hpz)] with the platinum complex [{PtIMe 3 } 4 ] affords mixtures of the heterodinuclear complexes [(η 6 - p -cymene)Ru(μ-pz) 3 PtMe 3 ] ( 1 ) and [(η 6 - p -cymene)Ru(μ-pz) 2 (μ-I)PtMe 3 ] ( 2 ). The reaction of the iridium derivative [Ir(η 5 -C 5 Me 5 )(pz) 2 (Hpz)] with [{PtIMe 3 } 4 ] gives [(η 5 -C 5 Me 5 )Ir(μ-pz) 2 (μ-I)PtMe 3 ] ( 3 ). Both [Ru(η 6 - p -cymene)(pz) 2 (Hpz)] and [Ir(η 5 -C 5 Me 5 )(pz) 2 (Hpz)] react with [{PtIMe 3 } 4 ] in the presence of NaOH yielding 1 and [(η 5 -C 5 Me 5 )Ir(μ-pz) 3 PtMe 3 ] ( 4 ), respectively. While [Ru(η 6 - p -cymene)(pz) 2 (Hpz)] reacts with [PtBr 2 Me 2 S x ] to give mixtures of [(η 6 - p -cymene)Ru(μ-pz) 3 PtBrMe 2 ] ( 5 ) and [(η 6 - p -cymene)Ru(μ-pz) 2 (μ-Br)PtBrMe 2 ] ( 6 ), the reaction of [Ir(η 5 -C 5 Me 5 )(pz) 2 (Hpz)] with [PtBr 2 Me 2 S x ] gives [(η 5 -C 5 Me 5 )Ir(μ-pz) 2 (μ-Br)PtBrMe 2 ] ( 7 ) as the sole product. All species were characterized in solution by 1 H-NMR spectroscopy. The crystal structure of complex 4 has been determined by single-crystal X-ray diffraction.

Diphenylphosphino(phenylthio)methane as a monodentate or bidentate chelate ligand in rhodium, iridium and ruthenium complexes, 3rystal structure of [(η5-C5Me5) IrCl(η2-Ph2PCH2SPhP,S)]BF4·Me2CO

Abstract Reactions of complexes [∗(η 5 - C 5 Me 5 ) MCl 2 ∗ 2 ] ( M = Rh, Ir ) and [∗(η 6 - MeC 6 H 4 Pr i ) RuCl 2 ∗ 2 ] with the ligand Ph2PCH2SPh in acetone solution led to neutral complexes with the general formula [(ring)MCl2(η1-Ph2PCH2SPhP)] (1–3). These compounds react with thallium tetrafluoroborate in acetone solution to yield new cationic complexes in which the ligand is acting in its chelate P,S-donor fashion, [(ring)MCl(η2-Ph2PCH2SPhP,S)]BF4 (4–6). When the removal of the chloride ligand in complexes 1–3 was carried out in the presence of a stoichiometric amount of Ph2PCH2SPh, cationic compounds containing two P-donor monodentate ligands of the type [(η5-C5Me5)MCl (η1-Ph2PCH2SPhP)2]BF4 (7 and 8) were obtained. The structure of the iridium derivative [(η5-C5Me5)IrCl(η2-Ph2PCH2SPhP,S)]BF4 · Me2CO has been determined by single-crystal X-ray diffraction methods. The complex cation contains a C5Me5 group occupying three coordination positions of a distorted octahedral iridium centre, a bidentate chelate P,S-bonded ligand and a chloride atom completing the coordination sphere.

Dithioethers as ligands in pentamethylcyclopentadienylrhodium(III) and iridium(III) complexes. Crystal structures of [{(η5-C5Me5)Rh}2(μ-Cl)2{μ-(MeS)2CH2}](BF4)2·H2O and [(η5-C5Me5)IrCl2{η1-(PhS)2CH2}]

Reactions of complexes [{(η 5 -C 5 Me 5 )MCl 2 } 2 ] (M=Rh, Ir) with the ligand (MeS) 2 CH 2 in CH 2 Cl 2 solution led to the neutral dinuclear complexes of the general formula [{(η 5 -C 5 Me 5 )MCl 2 } 2 {μ-(MeS) 2 CH 2 }] [M=Rh ( 1 ), Ir ( 2 )]. Compound 1 reacts in CH 2 Cl 2 solution with silver tetrafluoroborate in 1:2 molar ratio to yield the dinuclear cationic complex [{(η 5 -C 5 Me 5 )Rh} 2 (μ-Cl) 2 {μ-(MeS) 2 CH 2 }](BF 4 ) 2 ·H 2 O ( 3 ). Compound 2 reacts with silver salts in analogous conditions to give the mononuclear cationic complex [(η 5 -C 5 Me 5 )IrCl{η 2 -(MeS) 2 CH 2 }]BF 4 ( 4 ). Reactions of the starting complexes [{(η 5 -C 5 Me 5 )MCl 2 } 2 ] with the ligand (PhS) 2 CH 2 afforded the mononuclear complexes [(η 5 -C 5 Me 5 )MCl 2 (η 1 -(PhS) 2 CH 2 )] [M=Rh ( 5 ), Ir ( 6 )]. All the complexes have been characterised by analytical and spectroscopic means, and the fluxional behaviour of 4 , in solution, has been studied. The crystal structures of complexes 3 and 6 have been established by X-ray crystallography. Complex 3 crystallised in space group P 2 1 / n , a =11.848(2), b =12.693(2), c =21.608(4) A, β =95.18(2)° and Z =4. The complex cation consists of two (η 5 -C 5 Me 5 )Rh moieties connected by two chloride atoms and one dithioether group. The two rhodium atoms are separated by 3.6093(10) A. Complex 6 crystallised in space group P 2 1 / c , a =8.366(1), b =16.011(3), c =17.911(2) A, β =100.28(1)° and Z =4. The iridium atom has a distorted octahedral co-ordination with a η 5 -C 5 Me 5 group occupying the centre of three octahedral sites, two chloride atoms and a sulphur of a monodentate bis(phenylthio)methane ligand.

Platinum(II) complexes with dithiolates and phosphinites as ligands: crystal structure of [Pt{S2CO}{P(OMe)Ph2}2]

Abstract Reaction of the complex [PtCl{P(O)Ph2}{P(OH)Ph2}2] with silver or thallium derivatives of dithiolate ligands led to neutral complexes of general formula [Pt{S-S}{P(O)Ph2}{P(OH)Ph2}], where { SS } − = { S 2 CNEt 2 } − { S 2 P(OEt) 2 } − ( 2 ) and { S 2 COEt } − ( 3 ) . Complexes 2 and 3 reacted with an excess of NaI in acetone solution by dealkylation of the coordinated dithiolate ligand and formation of the compounds [Pt{S2P(O)(OEt)}{P(O)Ph2}{P(OH)Ph2}]Na (4) and [Pt{S2CO}{P(O)Ph2}{P(OH)P Na (5), respectively. The corresponding tetraphenylphosphonium derivatives (6, 7) were prepared by a metathetical reaction of these complexes with Ph4PBr in acetone solution. Related dithiolate complexes were obtained by reaction of the complex [Pt{S-S}2] with P(OMe)Ph2 in molar ratio 1 : 2. Thus, the reaction of [Pt{S2COEt}2] in dichloromethane solution at room temperature gave [Pt{S2COEt}{P(OMe)Ph2}2]Cl (8). This complex reacted with NaI in acetone to form the neutral compound [Pt{S2CO}{P(OMe)Ph2}2] (9). When the reaction was carried out in dichloromethane at reflux temperature using [Pt{S2P(OEt)2}2] as starting material, the neutral compound [Pt{S2P(O)(OEt)} {P(OMe)Ph2}2] (10) was obtained. The crystal structure of the complex 9 has been determined by X-ray diffraction. The neutral complex shows a nearly square-planar coordination of the metal and a planar dithiocarbonate ligand.

Synthesis and characterization of new dimethylplatinum(IV) complexes with o-(diphenylphosphino)thioanisole and its chalcogenide derivatives as ligands. Crystal structure of trans-[Me2PtBr2{o-Ph2P(S)C6H4SMeS,S′}]

Abstract The compound o-(diphenylphosphino)thioanisole can be oxidized by S or Se in benzene leading to the derivatives Ph2P(E)C6H4SMe [EPSMe; E=S (1), Se (2)]. These compounds act as bidentate chelate ligands in reactions with the platinum(IV) complex [Me2PtBr2]n to form trans and cis isomers of the general formula [Me2PtBr2(L2)] [L2=SPSMe (3, 4); SePSMe (5, 6)]. The reaction of the complex [Me2PtBr2]n with the starting ligand Ph2PC6H4SMe (PSMe) led to a reductive elimination affording the neutral complex [PtBr2(PSMe)] (7). The structure of the complex [Me2PtBr2{o-Ph2P(S)C6H4SMe}] was established by X-ray crystallography. The platinum atom has a distorted octahedral coordination and it is bonded to two methyl carbons, two bromide atoms and two sulfur atoms of the (o-diphenylphosphinesulfide)thioanisole bidentate ligand.

FIRST X-RAY CRYSTAL STRUCTURE OF A BIMETALLIC COMPLEX CONTAINING A p -COORDINATED HYDRAZONE: [(h 5-Cp)Fe(h 6-p-MeOC6H4)-NHN=CH-(h 5-C5H4)Fe(h 5-Cp)]+PF6

La hidrazona organometalica dinuclear [(h 5-Cp)Fe(h 6-p-MeO-C6H4)-NHN=CH-(h 5-C5H4)Fe(h 5-Cp)]+PF6- es preparada estereoquimicamente como su isomero trans por reaccion de la hidracina organometalica precursora [(h 5-Cp)Fe(h 6-p-MeO-C6H4)-NHNH2)]+PF6- con ferrocencarboxaldehido. Se ha determinado su estructura cristalina y molecular que consiste en dos sanwiches de hierro(II) del tipo [(h 5-Cp)Fe(h 6-areno)]+ y [(h 5-C5H4)Fe(h 5-Cp)] en posicion anti uno respecto del otro, los que se encuentran enlazados por un espaciador hidrazonico en forma de zig-zag