Novel Mercury Phosphanylamides

The reactions of bis(pentafluorophenyl)mercury, bis(diphenylphosphanyl)amine and neodymium or erbium metal in toluene yielded the subvalent mercury(1.33) complex [Hg 3 {μ 2 ‐(Ph 2 P) 2 N} 4 ] · 3 C 7 H 8 ( 1· 3 C 7 H 8 ) as a toluene solvate. Thecomplex was also prepared in high yield from Hg(C 6 F 5 ) 2 , (PPh 2 ) 2 NH and mercury metal in toluene at room temperature. From reaction of Hg(C 6 F 5 ) 2 and HN(PPh 2 ) 2 in toluene with no added metal, [Hg 2 {μ 2 ‐(Ph 2 P) 2 N} 2 {(Ph 2 P)(OPPh 2 )N} 2 ] · 2 C 7 H 8 ( 3· 2 C 7 H 8 ) has been obtained, and 3· 2 C 4 H 10 O 2 has also been isolated in low yield. From a related reaction, a solution of the product in CDCl 3 deposited [Hg 2 {μ 2 ‐(Ph 2 P) 2 N} 3 Cl] · 3/2 CDCl 3 ( 4· 3/2 CDCl 3 ). The structure of 1· 3 C 7 H 8 contains a Hg–Hg bonded Hg 3 triangle with adja‐cent metals bridged (P,P′) by either one or two phosphanyl‐amide ligands. One mercury is four coordinate, and the other two are five coordinate. In [Hg 2 {μ 2 ‐(Ph 2 P) 2 N} 2 {(Ph 2 P)(OPPh 2 )‐N} 2 ] · 2 S [S = C 7 H 8 or C 4 H 10 O 2 (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 {μ 2 ‐(Ph 2 P) 2 N} 3 Cl] · 3/2 CDCl 3 ( 4· 3/2 CDCl 3 ) with one mercury four coordinate and the other three. Three phosphanylamide ligands bridge (P,P′) the metals with a non‐bonding Hg ··· Hg separation of 3.0042(7) Å. Each HgP 3 array has a triangular arrangement, little affected in one case by the attachment of a chloride approximately normal to HgP 3 . (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)