Wiley InterScience Backfile Collection 1832-2000
Chemistry and Pharmacology
Reaction of Ni(COD)2 (COD = 1,5-cyclooctadiene) with two equivalents of Ph2PCH2CH2SnPh3 or of (Ph3P)2Pt(C2H4) with two equivalents of Ph2PCH2CH2SnR3 (R = Ph, Me, Bu) results in the immediate formation of the complexes (R3SnCH2CH2Ph2P)M[PPh2CH2CH2SnPh2(M-Sn)](R) (M = Ni, Pt) with a cis arrangement of the two phosphorus atoms. The structure of (Me3SnCH2CH2Ph2P)Pt[PPh2CH2-CH2SnMe2(Pt-Sn)](Me) was confirmed by an X-ray structure analysis. In the presence of PPh3, this complex shows dynamic behavior in solution due to Ph2PCH2CH2SnMe3/PPh3 exchange. When the phosphanylalkylstannanes Ph2PCH2CH2SnPh3-xMex (x = 1, 2) are employed in the reaction with Ni(COD)2 or (Ph3P)2Pt(C2H4), the Sn-Ph groups are more prone to oxidative addition than the Sn-Me groups. When Ni(COD)2 is treated with one equivalent of Ph2PCH2CH2SnPh3 and PR′3 (PCy3 or PMe2Ph) each, the complexes (R′3P)M(PPh2CH2CH2SnPh2)(Ph)(M-Sn) are formed. Heating of (Ph3SnCH2CH2Ph2P)Ni[PPh2-CH2CH2SnPh2(Ni-Sn)](Ph) to 70 °C induces the oxidative addition of a Sn-Ph group of the dangling ligand, and cis-Ni[PPh2CH2CH2SnPh2(Ni-Sn)]2 is obtained. The same complex is formed upon reaction of Ni(COD)2 with Ph2PCH2CH2SnPh2H. Reaction of Ni(COD)2 with Ph2PCH2CH2SnMe3 results in the immediate formation of trans-Ni[(PPh2CH2CH2SnMe2(Ni-Sn)]2.
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