Phosphoramidite complexes of Pd(II), Pt(II) and Rh(I): An effective hydrosilylation catalyst of 1-hexyne and 1-octene

Carroll Hannah K.; Parlane Fraser G. L.; Reich Noah; Jelier Benson J.; Montgomery Craig D.

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Phosphoramidite complexes of Pd(II), Pt(II) and Rh(I): An effective hydrosilylation catalyst of 1-hexyne and 1-octene

机译：Pd（II），Pt（II）和RH（i）的磷酰亚胺岩复合物：1-己炔和1-辛烯的有效氢化硅烷化催化剂

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The hydrophosphorane HP(OC6H4NMe)(2) was used to prepare the diastereotopic complexes [MCI2{P(OC6H4NMe)OC6H4NHMe}] (M = Pd, Pt) by reaction with [MCl2(PhCN)(2)], and [RhCI(PPh3){P(OC6H4NMe) OC6H4NHMe}] by reaction with [RhCl(PPh3)(3)]. To form these complexes, the phosphorane undergoes ring-opening, whereby it is coordinated as the tautomeric neutral phosphoramidite-amino chelating ligand. The crystal structure of [RhCI(PPh3){P(OC6H4NMe)OC6H4NHMe}] was determined and the geometry about the Rh(I) atom is square-planar with cis-disposed phosphorus-donor ligands. The Rh-P distance is shortened (2.1056(6) angstrom) due to Rh(d) -> P pi-backbonding. In addition, [RhCI(PPh3){P (OC6H4NMe)OC6H4NHMe}] was shown to be an effective regio- and stereoselective catalyst for the hydrosilylation of 1-octene and 1-hexyne. (C) 2017 Elsevier B.V. All rights reserved.

机译：通过与[MCl 2（PHCN）（2）]反应，使用疏水磷酸磷酸酯HP（OC6H4NME）（2）来制备非对抗络合物[MCI2 {P（OC6H4NME）OC6H4NHME}]（M = Pd，Pt），和[rhci（通过与[rhCl（PPH3）（3）]反应，PPH3）{P（OC6H4NME）oc6H4NHME}]。为了形成这些配合物，磷烷经历开环，由此与互变异构体磷酰胺胺 - 氨基螯合配体协调。确定[RHCI（PPH3）{P（OC6H4NME）OC6H4NHME}]的晶体结构，RH（I）原子的几何形状是方形平面，具有顺式磷的供体配体。由于RH（D） - > P PI-Backbonding，RH-P距离（2.1056（6）埃）缩短（2.1056（6）埃）。此外，[RHCI（PPH3）{P（OC6H4NME）OC6H4NHME}]显示为1-辛烯和1-己炔的氢化硅烷化的有效的序列和立体选择性催化剂。（c）2017年Elsevier B.V.保留所有权利。

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来源
《Inorganica Chimica Acta》 |2017年第2017期|共6页
作者
Carroll Hannah K.; Parlane Fraser G. L.; Reich Noah; Jelier Benson J.; Montgomery Craig D.;
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作者单位

Trinity Western Univ Dept Chem 7600 Glover Rd Langley BC V2Y 1Y1 Canada;

Trinity Western Univ Dept Chem 7600 Glover Rd Langley BC V2Y 1Y1 Canada;

Trinity Western Univ Dept Chem 7600 Glover Rd Langley BC V2Y 1Y1 Canada;

Simon Fraser Univ Dept Chem 8888 Univ Dr Burnaby BC V5A 1S6 Canada;

Trinity Western Univ Dept Chem 7600 Glover Rd Langley BC V2Y 1Y1 Canada;

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原文格式 PDF
正文语种 eng
中图分类无机化学;
关键词
Hydrosilylation; Phosphoramidite; Homogeneous catalysis; Diastereomers;

机译：乳硅烷化;磷酰亚胺岩;均匀催化;非对映异构体;

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1. Phosphoramidite complexes of Pd(II), Pt(II) and Rh(I): An effective hydrosilylation catalyst of 1-hexyne and 1-octene [J] . Carroll Hannah K., Parlane Fraser G. L., Reich Noah, Inorganica Chimica Acta . 2017,第期

机译：Pd（II），Pt（II）和RH（i）的磷酰亚胺岩复合物：1-己炔和1-辛烯的有效氢化硅烷化催化剂
2. Coordination of (#beta#-N-sulfonylaminoalkyl)phosphines and their analogous arsines to Pd~(II) and Pt~(II). Application of the Pd-complexes as chiral catalysts in asymmetric hydrosilylation of 1,3-dienes [J] . Magnus Gustafsson, Karl-Erik Bergqvist, Torbjorn Frejd Journal of the Chemical Society, Perkin Transactions 1 . 2001,第12期

机译：（＃β＃-N-磺酰基氨基烷基）膦及其类似的a氨酸与Pd〜（II）和Pt〜（II）的配位。钯配合物作为手性催化剂在1,3-二烯不对称氢化硅烷化中的应用
3. The effectiveness of rhodium(I),(II) and (III) complexes as catalysts in hydrosilylation of model olefin and polyether with triethoxysilane and poly(dimehtylsiloxane-co-mehtylsiloxane) [J] . TomaszGanicz, Ursazula mizerska, Monika Moszner, Applied Catalysis, A. General: An International Journal Devoted to Catalytic Science and Its Applications . 2004,第1期

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4. Bifunctional Selective Hydrosilylation of Terminal Alkynes by Bis(carbene)Iridium(III)and Rhodium(III)Complexes [C] . Luis A.Oro Annual Saudi-Japan Symposium on Technology in Petroleum Refining and Petrochemicals . 2018

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5. Part I. Asymmetric hydrosilylation of acetophenone using titanium catalysts. Part II. Synthesis of water-soluble palladacycles and their applications to the Suzuki reaction. Part III. Rhodium-catalyzed addition of aryl and alkenylboronic acids to aldehyde [D] . Huang, Rongcai. 2005

机译：第一部分：使用钛催化剂的苯乙酮不对称氢化硅烷化。第二部分水溶性palladacycles的合成及其在铃木反应中的应用。第三部分铑催化的芳基和烯基硼酸加成醛
6. bis-Nitrile and bis-Dialkylcyanamide Platinum(II) Complexes as Efficient Catalysts for Hydrosilylation Cross-Linking of Siloxane Polymers [O] . Regina M. Islamova, Mikhail V. Dobrynin, Daniil M. Ivanov, 2016

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机译：硫 - 氮螯合剂的金属配合物。 IV。 Ni（II），Pd（II），Pt（II）和Rh（III）的复合物，其具有2-氨基-1-环戊烯-1-碳酸二碳酸的甲酯
8. Synthesis and Reactivity of Cyclometalated Ni(II), Pd(II) and Pt(II) Complexes [R] . Beek, J. A. M. 1990

机译：环金属化Ni（II），pd（II）和pt（II）配合物的合成与反应性

Phosphoramidite complexes of Pd(II), Pt(II) and Rh(I): An effective hydrosilylation catalyst of 1-hexyne and 1-octene

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