| Abstract
| - The inter-triangular diphosphine bridge in [AuMn2(CO)8(μ-PPh2)]2(μ-P−P) turns into anintra-triangular one as it undergoes amine-oxide-promoted decarbonylation to give (P−P)AuMn2(CO)7(μ-PPh2) (P−P = Ph2P−X−PPh2; X = (CH2)n, Fe(C5H4)2; n = 1−4) in the presenceof the corresponding free diphosphine. The resultant triangular cluster contains a heterometallic Au−Mn bond overbridged by all common diphosphines attempted, including dppf(X = Fe(C5H4)2) and dppp (n = 3). The Au−Mn bond supported by dppf (2.6797(7) Å) isshorter than that supported by dppe (n = 2) (2.756(2) Å) or dppp (2.7643(4) Å).
- The inter-triangular diphosphine bridge in [AuMn2(CO)8(μ-PPh2)]2(μ-P−P) turns into an intra-triangular one as it undergoes amine-oxide-promoted decarbonylation to give (P−P)AuMn2(CO)7(μ-PPh2) (P−P = Ph2P−X−PPh2; X = (CH2)n, Fe(C5H4)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 diphospines attempted, including dppf (X = Fe(C5H4)2) and dppp (n = 3). A likely mechanism for the formation is proposed. 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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