Abstract

A benzene solution of trans-[Mo(N2)2(dppe)2] (1a; dppe = Ph2PCH2CH2PPh2) and an equimolar amount of dppe was heated at reflux for 2 h under Ar to give [Mo(P4)(dppe)] (2a; P4 = meso-o-C6H4(PPhCH2CH2PPh2)2), where the new linear tetraphosphine P4 is presumed to form through condensation of two dppe ligands in the coordination sphere of Mo. The W complex [W(P4)(dppe)] (2b) and its dppm analogue [W(P4)(dppm)] (dppm = Ph2PCH2PPh2) were also prepared from the reactions of trans-[W(N2)2(dppe)2] with one equiv of dppe or dppm in toluene at reflux for 2 h under Ar. Detailed structures of 2a and 2b were determined by X-ray crystallography. In contrast, when the reaction mixtures obtained by treatment of 1a with excess PR3 (R = Bun, Et) in place of dppe were cooled down to room temperature under N2, novel dinitrogen complexes containing the P4 ligand [Mo(N2)(P4)(PR3)] formed; these were characterized spectroscopically and by elemental analyses.

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