Record Details

A phosphomide based PNP ligand, 2,6-{Ph2PC(O)}(2)(C5H3N), showing PP, PNP and PNO coordination modes

DSpace at IIT Bombay

View Archive Info
 
 
Field Value
 
Title A phosphomide based PNP ligand, 2,6-{Ph2PC(O)}(2)(C5H3N), showing PP, PNP and PNO coordination modes
 
Creator KUMAR, P
KASHID, VS
REDDI, Y
MAGUE, JT
SUNOJ, RB
BALAKRISHNA, MS
 
Subject TRANSITION-METAL-COMPLEXES
PINCER-TYPE LIGANDS
H BOND ACTIVATION
AB-INITIO PSEUDOPOTENTIALS
ASYMMETRIC ALDOL REACTION
MOLECULAR-STRUCTURES
C-H
METHYL ISOCYANOACETATE
DENSITY FUNCTIONALS
RUTHENIUM COMPLEXES
 
Description A new class of PNP pincer ligands, pyridine-2,6-diylbis(diphenylphosphino)methanone, 2,6-{Ph2PC-(O)}(2)(C5H3N) (1) (hereafter referred to as "bis(phosphomide)"), was prepared by the reaction of picolinoyl-dichloride with diphenylphosphine in the presence of triethylamine. The bis(phosphomide) 1 shows symmetrical PNP, unsymmetrical PNO and simple bidentate PP coordination modes when treated with various transition metal precursors. The reaction between 1 and [Ru(p-cymene)Cl-2](2) in a 1 : 1 molar ratio yielded a binuclear complex [Ru2Cl4(NCCH3)(p-cymene){2,6-{Ph2PC(O)}(2)(C5H3N)}] (2) containing an unsymmetrical PNO pincer cage around one of the ruthenium centers, whereas the second ruthenium is bonded to the other phosphorus atom along with cymene and two chloride atoms. Symmetrical pincer complexes [RuCl(NCCH3)(2){2,6-{Ph2PC(O)}(2)(C5H3N)}](ClO4) (3), [Ru(eta(5)-C5H5){2,6-{Ph2PC(O)}(2)(C5H3N)}]-(OTf) (4) and [RhCl{2,6-{Ph2PC(O)}(2)(C5H3N)}] (5) were obtained in the respective reactions of 1 with [RuCl(NCCH3)(2)(p-cymene)](ClO4), [Ru(eta(5)-C5H5)Cl(PPh3)(2)] and [Rh(COD)Cl](2). Group 10 metal complexes [NiCl-{2,6-{Ph2PC(O)}(2)(C5H3N)}](BF4) (6), [PdCl{2,6-{Ph2PC(O)}(2)(C5H3N)}]ClO4 (7) and [PtCl{2,6-{Ph2PC-(O)}(2)(C5H3N)}] ClO4 (8) were obtained by transmetallation reactions of in situ generated Ag-I salts of 1 with Ni(DME)Cl-2 or M(COD)Cl-2 (M = Ni, Pd and Pt). The reactions between 1 and CuX or [Cu(NCCH3)(4)](BF4) produced mononuclear complexes of the type [CuX{2,6-{Ph2PC(O)}(2)(C5H3N)}] (9, X = Cl; 10, X = Br; 11, X = I), [Cu(NCCH3){Ph2C(O)}(2)(C5H3N)}](BF4) (12) and [Cu{Ph2C(O)}(2)(C5H3N)}(2)](BF4) (13). Similarly, the silver complexes [AgX{2,6-{Ph2PC(O)}(2)(C5H3N)}] (14, X = ClO4; 15, X = Br) were obtained by the treatment of 1 with AgClO4 or AgBr in 1 : 1 molar ratios. Treatment of 1 with AuCl(SMe2) in 1 : 1 and 1 : 2 molar ratios produced mono-and binuclear complexes, [AuCl{2,6-{Ph2PC(O)}(2)(C5H3N)}] (16) and [Au2Cl2{2,6-{Ph2PC(O)}(2)(C5H3N)}] (17), in good yield. The structures of ligand 1 and complexes 2, 5 and 17 were confirmed using single-crystal X-ray diffraction studies. DFT calculations were carried out to gain more insights into the structure and bonding features as well as feasibility of some key chemical transformations.
 
Publisher ROYAL SOC CHEMISTRY
 
Date 2016-01-15T06:52:07Z
2016-01-15T06:52:07Z
2015
 
Type Article
 
Identifier DALTON TRANSACTIONS, 44(9)4167-4179
1477-9226
1477-9234
http://dx.doi.org/10.1039/c4dt03960b
http://dspace.library.iitb.ac.in/jspui/handle/100/17979
 
Language en