Chiral Palladium(0) trans-Stilbene Complexes: Synthesis, Structure, and Oxidative Addition of Phenyl Iodide
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- 作者：Tim J. Brunker ; Natalia F. Blank ; Jillian R. Moncarz ; Corina Scriban ; Brian J. Anderson ; David S. Glueck ; Lev N. Zakharov ; James A. Golen ; Roger D. Sommer ; Christopher D. Incarvito ; and Arnold L. Rhei
- 刊名：Organometallics
- 出版年：2005
- 出版时间：May 23, 2005
- 年：2005
- 卷：24
- 期：11
- 页码：2730 - 2746
- 全文大小：351K
- 年卷期：v.24,no.11(May 23, 2005)
- ISSN：1520-6041
文摘
The chiral Pd(0) trans-stilbene complexes Pd(diphos*)(trans-stilbene) (diphos* = (R,R)-Me-Duphos, (R,R)-Et-Duphos, (R,R)-i-Pr-Duphos, (R,R)-Me-BPE, (S,S)-Me-FerroLANE, (S,S)-Me-DuXantphos, (S,S)-Et-FerroTANE, (R,S)-CyPF-t-Bu, (R,S)-PPF-t-Bu, (R,S)-BoPhoz) andNi((R,R)-Me-Duphos)(trans-stilbene) were prepared by NaBH(OMe)3 reduction of the corresponding M(diphos*)Cl2 compounds in the presence of trans-stilbene. The rate of oxidativeaddition of phenyl iodide to the stilbene complexes, which gave Pd(diphos*)(Ph)(I), dependedon the ligand (larger for increased ligand bite angles and reduced steric bulk) and wasmarkedly faster than oxidative addition to mixtures of Pd(dba)2 and diphos*. The complexesPd(diphos*)(Ph)(I) were prepared independently by treatment of PdL2(Ph)(I) (L2 = TMEDA,(PPh3)2) with diphos*. Oxidative addition of PhI to the complexes M((R,R)-Me-Duphos)(trans-stilbene) occurred in the rate order Pd > Ni 
f"> Pt. The complexes Pd(diphos*)Cl2, Pd(diphos*)(trans-stilbene), and Pd(diphos*)(Ph)(I), as well as some analogous Ni compounds, werestructurally characterized by X-ray crystallography.
f"> Pt. The complexes Pd(diphos*)Cl2, Pd(diphos*)(trans-stilbene), and Pd(diphos*)(Ph)(I), as well as some analogous Ni compounds, werestructurally characterized by X-ray crystallography.