Promotion of Tetrahedral Copper(I) Dimers by Chelation of 1,1'-Bis(diphenylphosphino)ferrocene (dppf). Crystal Structures of 2>(X = O2CH, I or NO3)

DOI: 10.1039/DT9940003451

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 3451 - 3458 (1994)

Update date:2022-08-05

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Authors:

Neo, Soh Ping

Zhou, Zhong-Yuan

Mak, Thomas C. W.

Hor, T. S. Andy

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Article abstract of DOI:10.1039/DT9940003451

Treatment of Cu(NO3)2 with 1,1'-bis(diphenylphosphino)ferrocene (dppf) gave <2> which readily exchanged NaO2CH or KI to gave <2> or <2>.X-Ray structural analysis of the complexes revealed three tetrahedral copper(I) dimers with nitrate, iodide or formate preferentially in bridging and dppf consistently in chelating modes.The P-Cu-P chelate angle in the nitrate <117.8(1) deg> is the largest of known dppf chelates in all geometries.These structures are different from their triphenylphosphine analogues which are all monomers.Exchanges of the nitrate complex with other carboxylates gave <n> (R = Me, CF3, Et, n-Pr or Ph).It also reacted with a stoichiometric amount of dppf to give .The geometrical influence of PPh3, Ph2PCH2PPh2 and dppf, and their preferred bonding modes to Cu(I) in relation to the complex nuclearity, are discussed.

Full text of DOI:10.1039/DT9940003451

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