SOLUTION STRUCTURE AND DYNAMICS OF 5-COORDINATE D6 COMPLEXES
SOLUTION STRUCTURE AND DYNAMICS OF 5-COORDINATE D6 COMPLEXES
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DOI：
10.1021/ja00848a012
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发表时间：
1975-01-01
影响因子：
15
通讯作者：
CAULTON, KG
中科院分区：
文献类型：
--
作者：
HOFFMAN, PR;CAULTON, KG
MX2 (PPh3) 3 (M= Ru, Os; X= Cl, Br) all exhibit square pyramidal (C2v) geometry in solution but undergo an intramolecular rearrangement which equilibrates the two phosphorus environments. The rearrangement barrier is higher for Os than Ru, a fact which correlates with the bond lengthchanges which accompany the rearrangement. The barrier for the bromo complex is larger than that of the chloro analog. RuCl2 (PPh3) 4 completely dissociates one phosphine in solution. RuCl2 (PPh3) 3 also dissociates triphenylphosphine to some extent, forming [RuCl2 (PPh3) 2] 2. OsX2 (PPh3) 3 does not exhibit detectable phosphine dissociation. RuHCl (PPh3) 3 also undergoes intramolecular rearrangement, but shows no dissociated phosphine. RuH (02CCH3)(PPh3) 3 shows neither rearrangement nor phosphine dissociation. RuCl2 (PPh3) 3 exchanges with free PPh3 by a dissociative mechanism. 3IP NMR parameters are reported for all complexes.Wilkinson and coworkers have synthesized a variety of catalytically active triphenylphosphine (L) complexes of ru-thenium (II). RuHClLg1 and RuH (02¿ R) L32 catalyze hy-drogenation and olefin isomerization. The former com-pound also catalyzes hydrosilylation3 and exchange of the metal-bound and olefinic protons. 4 While earlyreports showed hydrogenation catalysis when RuCl2L3 is the charged catalyst, the induction period observed suggests preliminary conversion to RuHClLs; RuCl2L3 is also observed to catalyze thehydrogenation of oxygento water. 5 RuCl2L3 promotes exchange of D2 with OH and NH bonds. 6 Olefin isomerization, 7· 8 oxidation of PPhs, 9 and alcoholysis of diarylsilanes3 are also catalyzed by RUCI2L3. At elevated temperatures in neat substrate, RuCl2L3 cata-
