Oligophosphan-Liganden, XXXIV** Organoplatin(II)-Komplexe mit (+)-(l S)-1,2-Bis(diphenylphosphino)- 1 -phenylethan-Koordination / Oligophosphine Ligands, XXXIV** Organoplatinum(II) Complexes with (+)-(1S)-1,2-Bis(diphenylphosphino)- 1-phenylethane Coordination

Abstract

Reaction of (C8H12)Pt(CH2CMe3)2 with ( + )-(1 S)-Ph2PCH(Ph)CH2PPh2, S-PHEPHOS, gave (S-PHEPHOS)Pt(CH2CMe3)2 (1). Cleavage of one of the Pt-C bonds of this compound with methanolic HCl yielded (S-PHEPHOS)PtCl(CH2CMe3) (2) which could be converted to (S-PHEPHOS)PtH(CH2CMe3) (3) by treatment with Na[HB(OMe)3], The complexes so obtained were characterized by NMR spectroscopy (preferentially 31P) as well as by an X-ray structure analysis performed on the dineopentyl derivative 1. While thermal generation of (S-PHEPHOS)Pt(0) from 3 in the presence of HC ≡ CC(O)OCMe3 produced the alkyne coordination compound (S-PHEPHOS)Pt(HC ≡ CC(O)OCMe3) (4) efficiently, thermolysis of 3 in the presence of PhC ≡ CH resulted in smooth trapping of the 14e intermediate to form the product of oxidative C - H addition, (S-PHEPHOS)PtH(C≡CPh) (5). In contrast, only indiscriminate reactions were observed to occur on thermal generation of (S-PHEPHOS)Pt(O) from neopentyl hydride 3 in C6H6 at 70 °C.