Synthesis and Structures of d10–d10 M2(μ‐dppm)2 Complexes with Sensitive Metal–Metal Distances in Response to the Binding of Sigma Donors |
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| Authors: | Ler‐Chun Shiu Shih‐An Liu Tian‐Shung Wu Kom‐Bei Shiu |
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| Institution: | 1. Department of Chemistry, National Cheng Kung University, Tainan 70101, Taiwan;2. School of Pharmacy, National Cheng Kung University, Tainan 70101, Taiwan |
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| Abstract: | Diphosphine‐bridged dicopper(I) acetate complexes Cu2(μ‐dppm)2(μ‐OAc)]X ( 2 X; X? =  ,  ) and Cu2(μ‐dppm)2(μ‐OAc)(MeCN)]X ( 4 X) were prepared and the structures of 2 (PF6 ) and 4 (PF6 ) determined by X‐ray crystallography. The ground‐state geometries of Cu2(μ‐dppm)2(μ‐OAc)]+ and Cu2(μ‐dppm)2(μ‐OAc)(L)]+ (L = py, MeCN, THF, acetone, MeOH) were also obtained using density functional theory (DFT). The increased Cu – Cu distances found experimentally and theoretically by comparing the structures of cation Cu2(μ‐dppm)2(μ‐OAc)]+ and its derivatives Cu2(μ‐dppm)2(μ‐OAc)(L)]+ reflect the binding of various sigma donors (L). When using Cu2(μ‐dppm)2(μ‐OAc)]+ as a structure sensor, the electron‐donating strength of a sigma donor can be quantitatively expressed as a DFT‐calculated Cu – Cu distance with the relative strength in the order py > MeCN > THF > acetone > MeOH, as determined. |
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| Keywords: | Copper Phosphane ligands Metal– metal interactions Donor– acceptor systems Supramolecular chemistry Density functional calculations |
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