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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.
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
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