In:
European Journal of Inorganic Chemistry, Wiley, Vol. 2008, No. 12 ( 2008-04), p. 1959-1968
Abstract:
Extended investigations of the reaction sequence [Cp′ 2 Nb(Te 2 )H]/CH 3 Li/[Co 2 (CO) 8 ] (Cp′ = t BuC 5 H 4 ) led to the identification of Li n [ 3 ] { 3 = [Co 9 Te 6 (CO) 8 ]; n = 1, 2} salts through their transformation with [PPN]Cl into [PPN] n [ 3 ] (PPN = Ph 3 PNPPh 3 ). These compounds form in the solid state columnar ([PPN][ 3 ]) or undulated 2D ([PPN] 2 [ 3 ]) supramolecular networks. Electrochemical studies of [Cp* 2 Nb(CO) 2 ][ 3 ] (Cp* = C 5 Me 5 ) or [Na(THF) 6 ][ 3 ] revealed the presence of the redox couples [ 3 ] – /[ 3 ] 2– /[ 3 ] 3– /[ 3 ] 4– /[ 3 ] 5– regardless of the nature of the cation, whereas in the anodic part oxidative degradation of the cluster takes place. This behavior is in agreement with the observation that [ 3 ] – containing salts form with PPh 3 AuCl or dppe decomposition products like [(PPh 3 ) 2 Au][CoCl 3 PPh 3 ] or [Co(CO) 2 dppe] 2 (μ‐Te). A neutral cluster comprising the Co@Co 8 (μ 4 ‐Te) 6 core formed in the reaction of [Cp* 2 Nb(CO) 2 ][Co 11 Te 7 (CO) 10 ] with PPh 3 AuCl, which gave [Co 9 Te 6 (CO) 4 (PPh 3 ) 4 ] ( 4 ) after oxidative cluster degradation and CO substitution. 4 was characterized by X‐ray crystallography. DFT calculations carried out on all members of the [ 3 ] n ( n = +1 to –5) family and on related species indicate that there is no significant Jahn–Teller distortion (and therefore no connectivity change) for any of the considered electron counts. Magnetic investigations on [PPN][ 3 ] show that the ground state of [ 3 ] – is a spin triplet with spins interacting antiferromagnetically in a 1D space.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
Type of Medium:
Online Resource
ISSN:
1434-1948
,
1099-0682
DOI:
10.1002/ejic.v2008:12
DOI:
10.1002/ejic.200701350
Language:
English
Publisher:
Wiley
Publication Date:
2008
detail.hit.zdb_id:
1475009-0
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