Dichlorobis[μ‐Methylenebis (Diphenyl‐Phosphine)]Dipalladium(I) (Pd–Pd)

Balch, Alan L.; Benner, Linda S.; Basil, John D.

doi:10.1002/9780470132593.ch87

Cited by 8 publications

(1 citation statement)

References 7 publications

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“…The complexes Pd 2 X 2 (dmpm) 2 (X = Cl ( 1a ), Br ( 1b ), I ( 1c ), the depm analogues ( 1a′ , 1b′ , 1c′ , and 1d′ ), Pd 2 Cl 2 (μ-CO)(dmpm) 2 , , Pd 2 Cl 2 (μ-CS 2 )(dmpm) 2 ( 5 ), , Pd 2 Cl 2 (dppm) 2 and Pd 2 I 2 (μ-S)(dppm) 2 , were prepared by the reported methods.…”

Section: Methodsmentioning

confidence: 99%

Reactions of the Bis(dialkylphosphino)methane Complexes Pd₂X₂(μ-R₂PCH₂PR₂)₂(X = halogen, R = Me or Et) with H₂S, S₈, COS, and CS₂; Detection of Reaction Intermediates

et al. 2011

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The Pd(2)X(2)(dmpm)(2) complexes [X = Cl (1a), Br (1b), I (1c); dmpm = bis(dimethylphosphino)methane. In all the dipalladium complexes mentioned in this paper, the dmpm, depm, and dppm ligands (unless stated otherwise) are bridging, but for convenience the μ-symbol is omitted.] react with H(2)S to yield H(2) and the bridged-sulfido complexes Pd(2)X(2)(μ-S)(dmpm)(2) (2a-c), of which 2a and 2b are structurally characterized. With 1a, two rapid reversible equilibria are observed by NMR spectroscopy below -30 °C, and two reaction intermediates are detected; both are likely hydrido(mercapto) species. Reaction of 1a with 1 equiv of elemental sulfur also yields 2a. The reaction of 1a with COS results in the initial formation of Pd(2)Cl(2)(μ-COS)(dmpm)(2) (3) that undergoes decarbonylation to yield 2a and Pd(2)Cl(2)(μ-CO)(dmpm)(2) (4), which is also formed via reversible insertion of the CO into the Pd-Pd bond of 1a. The solid-state molecular structure of the previously reported complex Pd(2)Cl(2)(μ-CS(2))(dmpm)(2) (5), together with solution NMR data for 3 and 5, reveal that the bridging heterocumulene ligands coordinate in an η(2)-C,S fashion. Analogous findings were made for the corresponding Pd(2)X(2)(depm)(2) complexes [X = Cl (1a'), Br (1b'), I (1c'); depm = bis(diethylphosphino)methane], although no μ-COS species was detected. The Pd(2)X(2)(μ-S)(depm)(2) complex was structurally characterized. Differences in the chemistry of the previously studied, corresponding dppm systems (dppm = bis(diphenylphosphino)methane) are discussed.

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Section: Methodsmentioning

confidence: 99%

Reactions of the Bis(dialkylphosphino)methane Complexes Pd₂X₂(μ-R₂PCH₂PR₂)₂(X = halogen, R = Me or Et) with H₂S, S₈, COS, and CS₂; Detection of Reaction Intermediates

et al. 2011

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Synthesis and Late Transition Metal Complexes of the Heterofunctional Phosphaneo-Ph2PNHC6H4P(S)Ph2

Aucott

Slawin

Woollins

2002

Eur. J. Inorg. Chem.

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The difunctional ligand o‐Ph2PNHC6H4P(S)Ph2 (PS) has been prepared by treatment of the lithium amide salt of 2‐(diphenylthiophosphanyl)aniline {2‐[Ph2P(S)]C6H4NH2} with Ph2PCl. The new ligand was oxidised to give the mixed chalcogen species Ph2P(E)NHC6H4P(S)Ph2, by treatment with H2O2 (where E = O) or aerial oxidation by recrystallisation from MeOH, and by reaction with Se8 (where E = Se) in warm toluene. The complexes [MCl(η3‐C3H5)(PS)] (M = Pt or Pd), cis‐[PtCl2(PS)(PMe2Ph)], [(AuCl)(PS)], cis‐[MCl2(PS)2] (M = Pt or Pd), cis‐[PtMe2(PS)2] and trans‐[PtMeCl(PS)2] have been synthesised by reaction of either [Pt(μ‐Cl)(μ‐η2:η1‐C3H5)]4, [Pd(μ‐Cl)(η3‐C3H5)]2, [{PtCl(μ‐Cl)(PMe2Ph)}2], [AuCl(tht)] (tht = tetrahydrothiophene), [PdCl2(cod)] or [PtX2(cod)] (X = Me or Cl; cod = cycloocta‐1,5‐diene) with (PS). In all these complexes the ligand (PS) is monodentate P‐bound. Chloride abstraction from [MCl(η3‐C3H5)(PS)] (M = Pt or Pd), cis‐[PtCl2(PS)(PMe2Ph)], cis‐[PtCl2(PS)2] and trans‐[PtMeCl(PS)2], using Ag[ClO4], gave the monocationic [M(η3‐C3H5)(PS)][ClO4] (M = Pt or Pd), cis‐[PtCl(PS)(PMe2Ph)][ClO4], trans‐[PtMe(PS)2][ClO4] or dicationic [Pt(PS)2][ClO4]2 compounds in which the ligand (PS) is κ2‐P,S‐bound. All compounds described here have been characterised by a combination of 31P{1H} and 1H NMR spectroscopy, microanalyses, FAB mass spectrometry and IR spectroscopy. The molecular structures of [AuCl(Ph2PNHC6H4P(S)Ph2‐P)] in which there is an intramolecular hydrogen‐bonding interaction between the amine proton and the sulfur atom of the thiophosphoryl group and trans‐[Pt(Ph2PNHC6H4P(S)Ph2‐κ2‐P,S)2][ClO4]2·CH2Cl2·2H2O in which the perchlorate counterions are associated by hydrogen‐bonding interactions to the amine protons of the κ2‐P,S ligands have been determined by single‐crystal X‐ray diffraction. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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The Preparation and Characterisation of Hetero‐ and Homobimetallic Complexes Containing Bridging Naphthalene‐1,8‐dithiolato Ligands

Aucott

Duerden

et al. 2006

Chemistry A European J

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Homo- and heterobimetallic complexes of the form [(PPh(3))(2)(mu(2)-1,8-S(2)-nap){ML(n)}] (in which (1,8-S(2)-nap)=naphtho-1,8-dithiolate and {ML(n)}={PtCl(2)} (1), {PtClMe} (2), {PtClPh} (3), {PtMe(2)} (4), {PtIMe(3)} (5) and {Mo(CO)(4)} (6)) were obtained by the addition of [PtCl(2)(NCPh)(2)], [PtClMe(cod)] (cod=1,5-cyclooctadiene), [PtClPh(cod)], [PtMe(2)(cod)], [{PtIMe(3)}(4)] and [Mo(CO)(4)(nbd)] (nbd=norbornadiene), respectively, to [Pt(PPh(3))(2)(1,8-S(2)-nap)]. Synthesis of cationic complexes was achieved by the addition of one or two equivalents of a halide abstractor, Ag[BF(4)] or Ag[ClO(4)], to [{Pt(mu-Cl)(mu-eta(2):eta(1)-C(3)H(5))}(4)], [{Pd(mu-Cl)(eta(3)-C(3)H(5))}(2)], [{IrCl(mu-Cl)(eta(5)-C(5)Me(5))}(2)] (in which C(5)Me(5)=Cp*=1,2,3,4,5-pentamethylcyclopentadienyl), [{RhCl(mu-Cl)(eta(5)-C(5)Me(5))}(2)], [PtCl(2)(PMe(2)Ph)(2)] and [{Rh(mu-Cl)(cod)}(2)] to give the appropriate coordinatively unsaturated species that, upon treatment with [(PPh(3))(2)Pt(1,8-S(2)-nap)], gave complexes of the form [(PPh(3))(2)(mu(2)-1,8-S(2)-nap){ML(n)}][X] (in which {ML(n)}[X]={Pt(eta(3)-C(3)H(5))}[ClO(4)] (7), {Pd(eta(3)-C(3)H(5))}[ClO(4)] (8), {IrCl(eta(5)-C(5)Me(5))}[ClO(4)] (9), {RhCl(eta(5)-C(5)Me(5))}[BF(4)] (10), {Pt(PMe(2)Ph)(2)}[ClO(4)](2) (11), {Rh(cod)}[ClO(4)] (12); the carbonyl complex {Rh(CO)(2)}[ClO(4)] (13) was formed by bubbling gaseous CO through a solution of 12. In all cases the naphtho-1,8-dithiolate ligand acts as a bridge between two metal centres to give a four-membered PtMS(2) ring (M=transition metal). All compounds were characterised spectroscopically. The X-ray structures of 5, 6, 7, 8, 10 and 12 reveal a binuclear PtMS(2) core with PtM distances ranging from 2.9630(8)-3.438(1) A for 8 and 5, respectively. The napS(2) mean plane is tilted with respect to the PtP(2)S(2) coordination plane, with dihedral angles in the range 49.7-76.1 degrees and the degree of tilting being related to the PtM distance and the coordination number of M. The sum of the Pt(1)coordination plane/napS(2) angle, a, and the Pt(1)coordination plane/M(2)coordination plane angle, b, a+b, is close to 120 degrees in nearly all cases. This suggests that electronic effects play a significant role in these binuclear systems.

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Dichlorobis[μ‐Methylenebis (Diphenyl‐Phosphine)]Dipalladium(I) (Pd–Pd)

Cited by 8 publications

References 7 publications

Reactions of the Bis(dialkylphosphino)methane Complexes Pd₂X₂(μ-R₂PCH₂PR₂)₂(X = halogen, R = Me or Et) with H₂S, S₈, COS, and CS₂; Detection of Reaction Intermediates

Reactions of the Bis(dialkylphosphino)methane Complexes Pd₂X₂(μ-R₂PCH₂PR₂)₂(X = halogen, R = Me or Et) with H₂S, S₈, COS, and CS₂; Detection of Reaction Intermediates

Synthesis and Late Transition Metal Complexes of the Heterofunctional Phosphaneo-Ph2PNHC6H4P(S)Ph2

The Preparation and Characterisation of Hetero‐ and Homobimetallic Complexes Containing Bridging Naphthalene‐1,8‐dithiolato Ligands

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Dichlorobis[μ‐Methylenebis (Diphenyl‐Phosphine)]Dipalladium(I) (Pd–Pd)

Cited by 8 publications

References 7 publications

Reactions of the Bis(dialkylphosphino)methane Complexes Pd2X2(μ-R2PCH2PR2)2(X = halogen, R = Me or Et) with H2S, S8, COS, and CS2; Detection of Reaction Intermediates

Reactions of the Bis(dialkylphosphino)methane Complexes Pd2X2(μ-R2PCH2PR2)2(X = halogen, R = Me or Et) with H2S, S8, COS, and CS2; Detection of Reaction Intermediates

Synthesis and Late Transition Metal Complexes of the Heterofunctional Phosphaneo-Ph2PNHC6H4P(S)Ph2

The Preparation and Characterisation of Hetero‐ and Homobimetallic Complexes Containing Bridging Naphthalene‐1,8‐dithiolato Ligands

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Reactions of the Bis(dialkylphosphino)methane Complexes Pd₂X₂(μ-R₂PCH₂PR₂)₂(X = halogen, R = Me or Et) with H₂S, S₈, COS, and CS₂; Detection of Reaction Intermediates

Reactions of the Bis(dialkylphosphino)methane Complexes Pd₂X₂(μ-R₂PCH₂PR₂)₂(X = halogen, R = Me or Et) with H₂S, S₈, COS, and CS₂; Detection of Reaction Intermediates