TY - JOUR
T1 - Dimolybdenum(II) complexes linked by axial cyano bridges to organic and organometallic ligands
T2 - Syntheses, structures, and characterization
AU - Xue, Wen Mei
AU - Kühn, Fritz E.
AU - Zhang, Guofang
AU - Herdtweck, Eberhardt
AU - Raudaschl-Sieber, Gabriele
PY - 1999/11/21
Y1 - 1999/11/21
N2 - Reaction of trans-[Mo2(μ-OAc)2(dppma)2(NCCH 3)n][BF4]2 (n = 0-2, dppma = bis(diphenylphosphino)methylamine) with a variety of ligands containing a nitrile group leads to axially substituted complexes of formula trans-[Mo2(μ-OAc)2(dppma)2(RCN) 2][BF4]n (n = 0, 2), R can be both an organic and an organometallic moiety. The obtained complexes are characterized by 1H-, 13C-, and 31P{1H}-NMR, IR, Raman, and UV/Vis spectroscopy, elemental analyses and cyclic voltammetry. Four of these complexes are additionally examined by single crystal X-ray analysis. The applied methods show that the axial ligands influence the spectroscopic and crystallographic data of the central moiety only slightly. However, while X-ray crystallography shows the MoMo quadruple bond length not to be significantly influenced by axial ligands, Raman spectroscopy gives a more detailed insight: organic ligands of the type NCR (R = CH3, t-Bu, C6H5 etc.) in axial positions weaken the MoMo interaction less than organometallic ligands of the type [NC-M(CO)5]- (M = Cr, Mo, W) and NCFe(CO)2Cp. UV/Vis examination indicates charge transfer from the organometallic axial ligands to the MoMo moiety.
AB - Reaction of trans-[Mo2(μ-OAc)2(dppma)2(NCCH 3)n][BF4]2 (n = 0-2, dppma = bis(diphenylphosphino)methylamine) with a variety of ligands containing a nitrile group leads to axially substituted complexes of formula trans-[Mo2(μ-OAc)2(dppma)2(RCN) 2][BF4]n (n = 0, 2), R can be both an organic and an organometallic moiety. The obtained complexes are characterized by 1H-, 13C-, and 31P{1H}-NMR, IR, Raman, and UV/Vis spectroscopy, elemental analyses and cyclic voltammetry. Four of these complexes are additionally examined by single crystal X-ray analysis. The applied methods show that the axial ligands influence the spectroscopic and crystallographic data of the central moiety only slightly. However, while X-ray crystallography shows the MoMo quadruple bond length not to be significantly influenced by axial ligands, Raman spectroscopy gives a more detailed insight: organic ligands of the type NCR (R = CH3, t-Bu, C6H5 etc.) in axial positions weaken the MoMo interaction less than organometallic ligands of the type [NC-M(CO)5]- (M = Cr, Mo, W) and NCFe(CO)2Cp. UV/Vis examination indicates charge transfer from the organometallic axial ligands to the MoMo moiety.
UR - http://www.scopus.com/inward/record.url?scp=33749104611&partnerID=8YFLogxK
U2 - 10.1039/a904742e
DO - 10.1039/a904742e
M3 - Article
AN - SCOPUS:33749104611
SN - 0300-9246
SP - 4103
EP - 4110
JO - Journal of the Chemical Society. Dalton Transactions
JF - Journal of the Chemical Society. Dalton Transactions
IS - 22
ER -