Functionalization of η<sup>1</sup>,η<sup>2</sup>-Bridging Cyaphide (C⋮P)<sup>-</sup> Ligands: Trinuclear η<sup>1</sup>,η<sup>1</sup>,η<sup>2</sup>-Bridging Cyaphide and Dinuclear Bridging Isocyaphide (C⋮PR) Complexes of Platinum
作者:Wayde V. Konze、Victor G. Young,、Robert J. Angelici
DOI:10.1021/om980746u
日期:1999.1.1
Cl(Et3P)2Pt(μ-η1,η2-C⋮P)Pt(PEt3)2 (II) in good yield, providing a much simpler and higher yield preparation of II, which was synthesized and characterized previously by a more circuitous route. Compound II reacts with 0.5 equiv of [Cl2Pt(PEt3)]2 or with 1 equiv of W(CO)5(THF) to generate the trinuclear metal−cyaphide complexes Cl(Et3P)2Pt[μ-η1,η1,η2-C⋮PPt(PEt3)(Cl)2}]Pt(PEt3)2 (III) and Cl(Et3P)2Pt[μ-η1
Palladium Coordination Compounds of σ<sup>3</sup>λ<sup>5</sup>-Phosphoranes: First Examples of Phosphonio−Methylene(imino)metallophosphorane [(R<sub>3</sub>P)(Me<sub>3</sub>Si)CP(ML<i><sub>n</sub></i>)NSiMe<sub>3</sub>] and Phosphonio−Methylene(oxo)phosphorane [(R<sub>3</sub>P)(Me<sub>3</sub>Si)CP(O)NSiMe<sub>3</sub>] Ligands
作者:Wayde V. Konze、Victor G. Young,、Robert J. Angelici
DOI:10.1021/om9801913
日期:1998.11.1
The oxidative addition reaction of Pd(PPh3)(4) with Cl2C=PN(SiMe3)(2) forms the phosphavinyl phosphonium complex Cl(Ph3P)Pd[eta(2)-C(Cl)(PPh3)=PN(SiMe3)(2)] (IIIa), which results from PPh3 migration from Pd to carbon in the eta(1)-phosphavinyl intermediate trans-Cl(Ph3P)(2)Pd-[C(Cl)=PN(SiMe3)(2)] (IIa). The reaction of Pd(dba)(dppe) with Cl2C=PN(SiMe3)(2) forms the eta(1)-phosphavinyl complex cis-Cl(dppe)Pd[C(Cl)=PN(SiMe3)(2)] (VI), which does not undergo phosphine migration. Compound IIIa undergoes substitution of the chloride ligand by PPh3 or MeCN in the presence of KPF6 to generate [(Ph3P)(2)Pd(eta(2)-C(Cl)(PPh3)=PN(SiMe3)(2))] (PF6) (IV) or [(Ph3P)(MeCN)Pd(eta(2)-C(Cl)(PPh3)=PN(SiMe3)(2))](PF6) (V), respectively; the structure of V was determined by X-ray diffraction studies. The reaction of Pd(PEt3)(4) with Cl2C= PN(SiMe3)(2) forms the eta(1)-phosphavinyl complex trans-Cl(Et3P)(2)Pd[C(Cl)=PN(SiMe3)(2)] (IIb), which does not undergo PEt3 migration. When 2 equiv of Pd(PEt3)(4) are reacted with Cl2C= PN(SiMe3)(2) the phosphonio-methylene(imino)metallophosphorane complex Pd(PEt3)(Cl)[mu-eta(1):eta(2)-C(SiMe3)(PEt3)=P=N(SiMe3)]Pd(PEt3)Cl (VIIa-b) forms as a 1:1 isomeric mixture. Compound VIIa-b reacts with MeI or NaI to generate Pd(PEt3)(I)[mu-eta(1):eta(2)-C(SiMe3)(PEt3)= P=N(SiMe3)]Pd(PEt3)I (VIIIa-b) and reacts with traces of water to generate Cl(Et3P)Pd-[eta(2)-C(SiMe3)(PEt3)=P(=O)NH(SiMe3)] (IX). The structure of VIIIb was partially determined, and the structure of IX was determined by X-ray diffraction studies. Compounds VIIa-b, VIIIa-b, and IX exhibit the first examples of coordinated methylene(imino, oxo)phosphorane ligands.