Synthesis and reactivity of ruthenium tetrazolate complexes containing a tris(pyrazolyl)borato (Tp) ligand
Resource
Journal of Organometallic Chemistry 693 (1): 117-127
Journal
Journal of Organometallic Chemistry
Journal Volume
693
Journal Issue
1
Pages
117-127
Date Issued
2008
Author(s)
Abstract
Facile ligand substitutions are observed when the neutral ruthenium cyclopropenyl complex (PPh3)[Ru]-C{double bond, long}C(Ph)CHCN (1, [Ru] = Tp(PPh3)Ru) is treated with MeCN and pyrazole yielding the nitrile substituted ruthenium cyclopropenyl complex (MeCN)[Ru]-C{double bond, long}C(Ph)CHCN (4a) and the ruthenium metallacyclic pyrazole complex (C3H3NN)[Ru]-C{double bond, long}C(Ph)CH2CN (7a), respectively. The reactions of Me3SiN3 with 1, 4a and 7a are investigated. Treatment of 1 with Me3SiN3 affords in high yield the cationic N-coordinated nitrile complex {(PPh3)[Ru]NCCH(Ph)CH2CN}N3 (3). Interestingly, the reaction of 4a with Me3SiN3 in CH2Cl2 in the presence of NH4PF6 results in an insertion of four nitrogen atoms into the Ru-Cα bond to form a diastereomeric mixture of the bright yellow zwitterionic tetrazolate complex (MeCN)[Ru]-N4CCH(Ph)CH2CN (6a) in a 3:2 ratio. The reaction of 7a with Me3SiN3 gives the zwitterionic tetrazolate complex (C3H3NNH)[Ru]-N4CCH(Ph)CH2CN (9a). The two cationic tetrazolate complexes {(C3H3NNH)[Ru]-N4(R)CCH(Ph)CH2CN}+ (12a, R = CH3, 12b, R = C6H5CH2) are prepared by electrophilic addition of organic halides to 9a. All of the complexes are identified by spectroscopic methods as well as elemental analysis. Pathways for the synthesis of these compounds are proposed. © 2007 Elsevier B.V. All rights reserved.
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