Z 865 IE] German version: Angew. Chem. 96 (1984) 621 'J(P,P)=66.3, 'J(P,H)=20.1 Hz; P=C-P); 'H-NMR (90 MHZ, C6D6): Angew. Chem. Int. Ed. Engl. 23 (1984) No. 8 0 Verlag Chemie GmbH, 0-6940 Weinheim, 1984 OS70/0833/84/

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The reactions of the phosphane [(Me3Si)2N](Ph)PCl with NaCpMo(CO)3 and NaCpW(CO)3 give the respective metallophosphenium complexes Cp(CO)2M{P(Ph)[N(SiMe3)2]} (M = Mo (4a), W (4b)). The subsequent reactions of 4a,b with S and Se produce unexpectedly different products:  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 have been fully characterized by elemental analyses and spectroscopic data, and the molecular structures of 4a, 7a,b, and 8a have been determined by single-crystal X-ray diffraction techniques. The molecular structure of 7a displays a long, terminal Mo−S bond, while 7b and 8a contain M−E−P three-membered rings.

The reaction of [(Me,Si),N](Ph)PW(CO),Cp with Fe2(CO)9 molecular structure consists of Fe(C0)3 and CpW(CO)p fragproduces in good yield the bimetallic compound ments joined by a bridging CO ligand and a phosphenium Cplb(C0)2(p-CO)Fe(CO),~(Ph)[N(SiMe,),] that was charac-ion fragment which comprise CI Pe-C-W-P four-membered terized by mass spectrometry, IR, lH-, and ,lP-NMR spectro-bicyclic structure.scopy, and single crystal X-ray diffraction analysis. TheIt is well-known that reactions of many monochlorophosphanes, The chemical reactivity of these species is of interest[1p4] because the patterns that evolve may help elucidate additional details of the electronic structures of 1 and 2. In particular, Malisch and coworkers[2] have observed that several examples of 1 combine with Fe2(C0)9. They proposed that the resulting complexes 3 have threemembered heterocyclic structures, although characterization details have not yet appeared in the literature. Such behavior suggests that the phosphorus atom in I retains considerable nucleophilic activity consistent with our ob~ervation[~q that CpMo-(CO),P(Ph)[N(SiMe,),] l a reacts smoothly with H3B . THF and forms the novel complex 4. This structure was crystallographically confirmed, and extended Hiickel calculations for a model compound revealed a rational justification for the unique Mo-H-B bridging interaction. These resuits also suggest that perhaps a related M-C(0)-Fe bridging interaction might take place in complexes such as 3. We report here the synthesis of C p s CO)Fe(CO),P(Ph)[N(SiMe,),l 5 and its molecular structure determination, which confirms the formation of a four-membered W -C(0) -Fe-P bicycle.The reaction of CpW(CO),P(Ph)[N(SiMe3)z] la and F e~( c 0 )~ in a 1 : 1 ratio results in addition of an Fe(CO)4 fragment to the metallophosphenium complex, as shown in the equation. Compound 5 is a dark red crystalline solid that melts in the range 122-125°C and is indefinitely stable in the absence of air and moisture. The composition was confirmed by elemental analysis and mass spectrometry. The EI-MS of 5 in the high mass region is complicated by the presence of four abundant W isotopes; however, a weak parent ion envelope (mle 745-740) is detected as are envelopes for (M-CO'), (M-2 / y a