The inter-triangular diphosphine bridge in [AuMn 2 (CO) 8 (µ-PPh 2 )] 2 (µ-P-P) turns into an intra-triangular one as it undergoes amine-oxide-promoted decarbonylation to give (P-P)-AuMn 2 (CO) 7 (µ-PPh 2 ) (P-P ) Ph 2 P-X-PPh 2 ; X ) (CH 2 ) n , Fe(C 5 H 4 ) 2 ; n ) 1-4) in the presence of the corresponding free diphosphine. The resultant triangular cluster contains a heterometallic Au-Mn bond overbridged by all common diphosphines attempted, including dppf (X ) Fe(C 5 H 4 ) 2 ) and dppp (n ) 3). The Au-Mn bond supported by dppf (2.6797(7) Å) is shorter than that supported by dppe (n ) 2) (2.756(2) Å) or dppp (2.7643(4) Å).
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