| Abstract
| - The reactions of the phosphane[(Me3Si)2N](Ph)PCl withNaCpMo(CO)3 andNaCpW(CO)3give the respective metallophosphenium complexesCp(CO)2M{P(Ph)[N(SiMe3)2]}(M = Mo(4a), W (4b)). The subsequent reactions of4a,b with S and Se produce unexpectedlydifferentproducts: Cp(CO)2(S)M{P(Ph)[N(SiMe3)2]}(M = Mo (7a));Cp(CO)2MSP(Ph)[N(SiMe3)2](M= W (7b));Cp(CO)2MSeP(Ph)[N(SiMe3)2](M = Mo (8a), W (8b)). The compounds havebeenfully characterized by elemental analyses and spectroscopic data, andthe molecularstructures of 4a, 7a,b, and8a have been determined by single-crystal X-raydiffractiontechniques. The molecular structure of 7a displays along, terminal Mo−S bond, while 7band 8a contain M−E−P three-memberedrings.
- The reactions of sulfur and seleniumwithCpM(CO)2{P(Ph)[N(SiMe3)2]}(M = Mo, W) have been examined and found to give two classes ofaddition products. With E = S and M = Mo the product containsa long Mo−S terminal bond while the products with E = Se, M = Moand E = S and Se, M = W contain a M−E−Pthree-membered ring.
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