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Chan EY, Zhang QF, Sau YK, Lo SM, Sung HH, Williams ID, Haynes RK, Leung WH: Chiral bisphosphinite metalloligands derived from a P-chiral secondary phosphine oxide. Inorg Chem. 2004 Aug 9;43(16):4921-6.
Interaction of PdCl (2)(MeCN)(2) with 2 equiv of (S (P))-(t) BuPhP (O) H (1H) followed by treatment with Et (3) N gave [Pd ((1)(2) H)](2)(micro-Cl)(2) (2). Reaction of 2 with Na [S (2) CNEt (2)] or K [N (PPh (2) S)(2)] afforded Pd [(1)(2) H](S (2) CNEt (2)) (3) or Pd [(1)(2) H)[N (PPh (2) S)(2)] (4), respectively. Treatment of 3 with V (O)(acac)(2) (acac = acetylacetonate) and CuSO (4) in the presence of Et (3) N afforded bimetallic complexes V (O)[Pd (1)(2)(S (2) CNEt (2))](2) (5) or Cu [Pd (1)(2)(S (2) CNEt (2))](2) (6), respectively. X-ray crystallography established the S (P) configuration for the phosphinous acid ligands in 3 and 6, indicating that 1H binds to Pd (II) with retention of configuration at phosphorus. The geometry around Cu in 6 is approximately square planar with the average Cu-O distance of 1.915 (3) A. Treatment of 2 with HBF (4) gave the BF (2)-capped compound [Pd ((1)(2) BF (2))](2)(micro-Cl)(2) (7). The solid-state structure of 7 containing a PdP (2) O (2) B metallacycle has been determined. Chloride abstraction of 7 with AgBF (4) in acetone/water afforded the aqua compound [Pd ((1)(2) BF (2))(H (2) O)(2)][BF (4)] (8) that reacted with [NH (4)](2)[WS (4)] to give [Pd ((1)(2) BF (2))(2)](2)[micro-WS (4)] (9). The average Pd-S and W-S distances in 9 are 2.385 (3) and 2.189 (3) A, respectively. Treatment of [(eta (6)-p-cymene) RuCl (2)](2) with 1H afforded the phosphinous acid adduct (eta (6)-p-cymene) RuCl (2)(1H) (10). Reduction of [CpRuCl (2)](x)() (Cp = eta (5)-C (5) Me (5)) with Zn followed by treatment with 1H resulted in the formation of the Zn (II) phosphinate complex [(CpRu (eta (6)-C (6) H (5)))(t) BuPO (2))](2)(ZnCl (2))(2) (11) that contains a Zn (2) O (4) P (2) eight-membered ring. |
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