Novel mercury phosphanylamides

作者：Cole ML; Deacon GB; Junk PC; Konstas K; Roesky PW

来源：European Journal of Inorganic Chemistry, 2005, (6): 1090-1098.

DOI：10.1002/ejic.200400932

• mercury
• redox transmetallation
• phosphanylamide ligands
• subvalent complexes
• P donors

The reactions of his (pentafluorophenyl)mercury, bis(diphenylphosphanyl)amine and neodymium or erbium metal in toluene yielded the subvalent mercury(1.33) complex [Hg-3{mu(2)-(Ph2P)(2)N}(4)](.)3C(7)H(8) (1(.)3 C7H8) as a toluene solvate. The complex was also prepared in high yield from Hg(C6F5)(2), (PPh2)(2)NH and mercury metal in toluene at room temperature. From reaction of Hg(C6F5)(2) and HN(PPh2)(2) in toluene with no added metal, [Hg-2{mu(2)-(Ph2P)(2)N}(2){(Ph2P)(OPPh2) N}(2)](.)2C(7)H(8) (3(.)2C(7)H(8)) has been obtained, and 3(.)2C(4)H(10)O(2) has also been isolated in low yield. From a related reaction, a solution of the product in CDCl3 deposited [Hg-2{mu(2)-(Ph2P)(2)N}(3)Cl](.)3/2CDCl(3) (4(.)3/2CDCl(3)). The structure of 1(.)3C(7)H(8) contains a Hg-Hg bonded Hg-3 triangle with adjacent metals bridged (P,P') by either one or two phosphanylamide ligands. One mercury is four coordinate, and the other two are five coordinate. In [Hg-2{mu(2)-(Ph2P)(2)N}(2){(Ph2P)(OPPh2)N}(2)](.)2S [S = C7H8 or C4H10O2 (1,2-dimethoxyethane)], the mercury atoms are bridged (P,P') by two phosphanylamide ligands, whilst the hemi-oxidised ligands are chelating (O,P) in a transoid disposition to each other leading to four coordination. There is unsymmetrical ligation in [Hg-2{mu(2)-(Ph2P)(2)N}(3)Cl](.)3/2 CDCl3 (4(.)3/2 CDCl3) with one mercury four coordinate and the other three. Three phosphanylamide ligands bridge (P,P') the metals with a non-bonding (HgHg)-Hg-... separation of 3.0042(7) angstrom. Each HgP3 array has a triangular arrangement, little affected in one case by the attachment of a chloride approximately normal to Hgp(3).

• 出版日期2005-3-18