Insertion of a Nontrigonal Phosphorus Ligand into a Transition Metal-Hydride: Direct Access to a Metallohydrophosphorane

被引：28

作者：

Tanushi, Akira ^{[1
]}

Radosevich, Alexander T. ^{[1
]}

机构：

[1] MIT, Dept Chem, 77 Massachusetts Ave, Cambridge, MA 02139 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2018年 / 140卷 / 26期

关键词：

RAY CRYSTAL-STRUCTURE; H OXIDATIVE ADDITION; MOLECULAR-STRUCTURE; SUBSTITUTION-REACTIONS; RUTHENIUM COMPLEXES; CHEMISTRY; PLATINUM(II); REACTIVITY; EXCHANGE; REDOX;

D O I：

10.1021/jacs.8b05156

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The synthesis and reactivity of an NPN-chelating ligand containing a nontrigonal phosphorous triamide center (L1 = P(N(o-N(2-pyridyl)C6H4)(2)) is reported. Metalation of L1 with RuCl2 (PPh3)(3) gives RuCl2 (PPh3)-(L1) (2). By contrast, metalation of Ll with RuHCl-(CO)(PPh3)(3) yields RuCl(CO)(PPh 3)(L1(H)) (3), a chelated 10-P-5 ruthenahydridophosphorane, via net insertion into the Ru-H bond. Hydride abstraction from 3 with Ph3CPF6 gives [RuCl(CO)(PPh3)(L1)]PF6 (4); reaction of 4 with NaBH4 returns 3.

引用

页码：8114 / 8118

页数：5

共 50 条

[21] KINETICS AND MECHANISM OF CO2 INSERTION INTO A METAL-HYDRIDE BOND - A LARGE SOLVENT EFFECT AND AN INVERSE KINETIC ISOTOPE EFFECT
SULLIVAN, BP
MEYER, TJ
ORGANOMETALLICS, 1986, 5 (07) : 1500 - 1502
[22] Catalytic Hydrogenation of Carbon Dioxide with a Highly Active Hydride on Ir(III)-Pincer Complex: Mechanism for CO2 Insertion and Nature of Metal-Hydride Bond
Li, Jun
Yoshizawa, Kazunari
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 2011, 84 (10) : 1039 - 1048
[23] HYDRIDE AND HALIDE LIGAND EFFECTS ON THE ENTHALPIES OF PROTONATION OF TRANSITION-METAL COMPLEXES
ROTTINK, MK
ANGELICI, RJ
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (21) : 8296 - 8298
[24] Mechanistic Studies of Alkyne Hydroboration by a Well-Defined Iron Pincer Complex: Direct Comparison of Metal-Hydride and Metal-Boryl Reactivity
Narro, Ana L.
Arman, Hadi D.
Tonzetich, Zachary J.
INORGANIC CHEMISTRY, 2022, 61 (27) : 10477 - 10485
[25] PHOSPHORUS TRIOXIDE AS A TETRADENTATE LIGAND .I. TRANSITION METAL COMPLEXES
RIESS, JG
VANWAZER, JR
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1966, 88 (10) : 2166 - &
[26] EVIDENCE FOR MIGRATORY INSERTION OF A METHYLIDENE LIGAND INTO A TRANSITION METAL-METHYL BOND
HAYES, JC
PEARSON, GDN
COOPER, NJ
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (15) : 4648 - 4650
[27] EVIDENCE FOR INSERTION OF A COORDINATED METHYLENE LIGAND INTO A TRANSITION-METAL ALKYL LINKAGE
HAYES, JC
PEARSON, GDN
COOPER, NJ
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 1981, 181 (MAR): : 64 - INOR
[28] Estimating the Acidity of Transition Metal Hydride and Dihydrogen Complexes by Adding Ligand Acidity Constants
Morris, Robert H.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2014, 136 (05) : 1948 - 1959
[29] Surface ligand stabilizes interstitial hydrogen in 2D transition metal hydride
Lv, Fan
Guo, Shaojun
MATTER, 2023, 6 (11) : 3693 - 3695
[30] O2 Insertion into Group 9 Metal-Hydride Bonds: Evidence for Oxygen Activation through the Hydrogen-Atom-Abstraction Mechanism
Keith, Jason M.
Teets, Thomas S.
Nocera, Daniel G.
INORGANIC CHEMISTRY, 2012, 51 (17) : 9499 - 9507

← 1 2 3 4 5 →