Carbon Hydrogen versus Nitrogen Oxygen Bond Activation in Reactions of N-Oxide Derivatives of 2,2′-Bipyridine and 1,10-Phenanthroline with a Dimethylplatinum(II) Complex

被引：38

作者：

Moustafa, Mohamed E. ^{[1
,2
]}

Boyle, Paul D. ^{[1
]}

Puddephatt, Richard J. ^{[1
]}

机构：

[1] Univ Western Ontario, Dept Chem, London, ON N6A 5B7, Canada

[2] Suez Canal Univ, Dept Chem, Fac Educ, Arish, Egypt

来源：

ORGANOMETALLICS | 2014年 / 33卷 / 19期

基金：

加拿大自然科学与工程研究理事会;

关键词：

TRANSITION-METAL-COMPLEXES; C-H BOND; CYCLOMETALATED ORGANOPLATINUM COMPLEXES; OXIDATIVE ADDITION; PLATINUM(II) COMPLEXES; DIBENZOYL PEROXIDE; ALKYL-HALIDES; LIGAND; CHEMISTRY; MECHANISM;

D O I：

10.1021/om500712e

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The reactions of the potential oxygen atom donor ligands 1,10-phenanthroline N-oxide (phenO) and 2,2-bipyridine N-oxide (bipyO) with the dimethylplatinum(II) complex [Pt2Me4(mu-SMe2)(2)] are reported. The reaction with the more rigid ligand phenO gave [PtMe2(2N,O-phenO)], which underwent oxidative addition with 4-t-Bu-C6H4CH2Br to give the platinum(IV) complex [PtBrMe2(CH2C6H4-4-t-Bu)(phenO)]. The complex [PtMe2(phenO)] reacted with methanol in air to give [Pt(OH)(OMe)Me-2(phenO)], but under an inert atmosphere it gave [Pt(OH)(OMe)Me-2(phen)], in a reaction involving NO bond activation. In contrast, the reaction of [Pt(2)Me4(mu-SMe2)(2)] with bipyO occurred by CH bond activation to give methane and [PtMe(kappa N-2,C-C5H4N-C5H3NO)(SMe2)], which underwent ligand substitution with pyridine, triphenylphosphine, or bis(diphenylphosphino)methane (dppm) to give [PtMe(kappa N-2,C-C5H4N-C5H3NO)(NC5H5)], [PtMe(kappa N-2,C-C5H4N-C5H3NO)(PPh3)], or the binuclear [{PtMe(kappa N-2,C-C5H4N-C5H3NO)}2(?-dppm)], respectively. With bis(diphenylphosphino)ethane (dppe), ligand substitution gave [PtMe(kappa C-1-C5H4N-C5H3NO)(dppe)], which contains a monodentate metalated bipyO ligand. The mechanisms of the key reactions are discussed.

引用

页码：5402 / 5413

页数：12

共 25 条

[21] Cyclometalated platinum(II) complexes of 2,2'-bipyridine N-oxide containing a 1,1'-bis(diphenylphosphino) ferrocene ligand: structural, computational and electrochemical studies
Shahsavari, Hamid R.
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[22] XPS, single crystal X-ray diffraction and cyclic voltammetric studies on 1,10-phenanthroline and 2,2′-bipyridine adducts of bis(piperidinecarbodithioato-S,S′)cadmium(II) with CdS4N2 environment - A stereochemical and electronic distribution investigation
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[23] On the synthesis and structures of the complexes [RuCl(L)(dppb)(N-N)]PF6 (L = CO, py or 4-NH2py; dppb=1,4-bis(diphenylphosphino)butane; N-N=2,2′-bipyridine or 1,10-phenanthroline) and [(dppb)(CO)Cl2-Ru-pz-RuCl2(CO)(dppb)] (pz = pyrazine)
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[24] Thermal C-H Bond Activation of Benzene with Cationic [Pt(CX3(L)]+ Complexes in the Gas Phase: A Combined Experimental/Theoretical Study (X = H, D; L=1,10-Phenanthroline, 2,2′-Bipyrimidine, 2,2′-Bipyridine, and (o,o′-Cl2C6H3)N=C(CH3)-C(CH3)=N(o,o′-Cl2C6H3))
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[25] Synthesis and crystal structure of a 3D copper(II)-silver(I) coordination polymer assembled through hydrogen bonding, π-π stacking and metal-π interactions, {[Cu(phen)2(CN)][Ag(CN)2] • 3H2O}n (phen=1,10-phenanthroline)
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ZEITSCHRIFT FUR NATURFORSCHUNG SECTION B-A JOURNAL OF CHEMICAL SCIENCES, 2015, 70 (07): : 455 - 459

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