Toggle Main Menu Toggle Search

Open Access padlockePrints

Kinetic studies on the reactions of HCl with trans-[MoL(CNPh)(Ph2PCH2CH2PPh2) 2] (L=N2, H2 or CO)

Lookup NU author(s): Professor Richard Henderson

Downloads

Full text for this publication is not currently held within this repository. Alternative links are provided below where available.


Abstract

The kinetics of the reactions between anhydrous HCl and trans-[MoL(CNPh)(Ph2PCH2CH2PPh2) 2] (L=CO, N2 or H2) have been studied in thf at 25.0°C. When L=CO, the product is [MoH(CO)(CNPh)(Ph2PCH2CH2PPh2) 2]+, and when L=H2 or N2 the product is trans-[MoCl(CNHPh)(Ph2PCH2CH2PPh 2)2]. Using stopped-flow spectrophotometry reveals that the protonation chemistry of trans-[MoL(CNPh)(Ph2PCH2CH2PPh2) 2] is complicated. It is proposed that in all cases protonation occurs initially at the nitrogen atom of the isonitrile ligand to form trans-[MoL(CNHPh)(Ph2PCH2CH2PPh 2)2]+. Only when L=N2 is this single protonation sufficient to labilise L to dissociation, and subsequent binding of Cl- gives trans-[MoCl(CNHPh)(Ph2PCH2CH2PPh 2)2]. At high concentrations of HCl a second protonation occurs which inhibits the substitution. It is proposed that this second proton binds to the dinitrogen ligand. When L=CO or H2, a second protonation is also observed but in these cases the second protonation is proposed to occur at the carbon atom of the aminocarbyne ligand, generating trans-[MoL(CHNHPh)(Ph2PCH2CH2PPh 2)2]2+. Addition of the second proton labilises the trans-H2 to dissociation, and subsequent rapid binding of Cl- and dissociation of a proton yields the product trans-[MoCl(CNHPh)(Ph2PCH2CH2PPh 2)2]. Dissociation of L=CO does not occur from trans-[Mo(CO)(CHNHPh)(Ph2PCH2CH2PPh 2)2]2+, but rather migration of the proton from carbon to molybdenum, and dissociation of the other proton produces [MoH(CO)(CNPh)(Ph2PCH2CH2PPh2) 2]+. © 2002 Elsevier Science B.V. All rights reserved.


Publication metadata

Author(s): Rosenblat M-C, Henderson RA

Publication type: Article

Publication status: Published

Journal: Inorganica Chimica Acta

Year: 2002

Volume: 331

Issue: 1

Pages: 270-278

ISSN (print): 0020-1693

ISSN (electronic): 1873-3255

Publisher: Elsevier BV

URL: http://dx.doi.org/10.1016/S0020-1693(01)00819-2

DOI: 10.1016/S0020-1693(01)00819-2


Altmetrics

Altmetrics provided by Altmetric


Share