TY - JOUR
T1 - 1,3-ditungstacyclobutadienes. 2. the Synthesis of Alkoxide Derivatives of W2(μ-csime3)2(ch2sime3)4 and Investigations of the Electronic Structures of the M2(μ-csime3)2 core as a Function of Dn-dninteractions (n = 0, M = Ta; N = 1, M = W; N = 2, M = Re)
AU - Chisholm, Malcolm H.
AU - Heppert, Joseph A.
AU - Kober, Edward M.
AU - Lichtenberger, Dennis L.
PY - 1987/5/1
Y1 - 1987/5/1
N2 - W2(μ-CSiMe3)2(CH2SiMe3)4(I) reacts with t-BuOH in alkane solvents to produce a mixture of two isomers of W2(μ-CSiMe)2(O-t-Bu)2(CH2SiMe3)2from which the minor isomer can be isolated by fractional crystallization. the electronic structures of several related dimetallacyclobutadiene derivatives have been investigated by UV photoelectron spectroscopy, UV/visible spectrophotometry, and MO calculations. the M-M bonding configurations for the M2(μ-CSiMe3)2(CH2SiMe3)4molecules have been determined as σ°δ*°, σ2δ*0, and σ2δ*2for M = Ta, W, and Re, respectively, by EHMO and Fenske-Hall MO calculations. This result is better reconciled with the previously observed M-M distances—Nb2> Re2> W2—than with the original proposal of a σ 2 π 2 configuration for the Re derivative. On replacement of the terminal alkyl ligands of the W complex by O-i-Pr ligands, the 2auLUMO (W-W δ*) and 2b2g w- μ -c π bond are strongly destabilized by antibonding interactions with pπ orbitals on oxygen. Destabilizaμon of the 2b2gorbital results in the appearance of a clearly defined ionization representing this orbital at 7.2 eV in the PE spectrum of W2(μ-CSiMe3)2(0-i-Pr)4. Mulliken population analyses of the 6ag orbitals of I and W2(μ-CSiMe3)2(0-i-Pr)4 correctly predict that I prefers a shorter W-W distance of 2.54 A, while the alkoxide-substituted compound prefers the longer W-W distance of 2.62 A.
AB - W2(μ-CSiMe3)2(CH2SiMe3)4(I) reacts with t-BuOH in alkane solvents to produce a mixture of two isomers of W2(μ-CSiMe)2(O-t-Bu)2(CH2SiMe3)2from which the minor isomer can be isolated by fractional crystallization. the electronic structures of several related dimetallacyclobutadiene derivatives have been investigated by UV photoelectron spectroscopy, UV/visible spectrophotometry, and MO calculations. the M-M bonding configurations for the M2(μ-CSiMe3)2(CH2SiMe3)4molecules have been determined as σ°δ*°, σ2δ*0, and σ2δ*2for M = Ta, W, and Re, respectively, by EHMO and Fenske-Hall MO calculations. This result is better reconciled with the previously observed M-M distances—Nb2> Re2> W2—than with the original proposal of a σ 2 π 2 configuration for the Re derivative. On replacement of the terminal alkyl ligands of the W complex by O-i-Pr ligands, the 2auLUMO (W-W δ*) and 2b2g w- μ -c π bond are strongly destabilized by antibonding interactions with pπ orbitals on oxygen. Destabilizaμon of the 2b2gorbital results in the appearance of a clearly defined ionization representing this orbital at 7.2 eV in the PE spectrum of W2(μ-CSiMe3)2(0-i-Pr)4. Mulliken population analyses of the 6ag orbitals of I and W2(μ-CSiMe3)2(0-i-Pr)4 correctly predict that I prefers a shorter W-W distance of 2.54 A, while the alkoxide-substituted compound prefers the longer W-W distance of 2.62 A.
UR - http://www.scopus.com/inward/record.url?scp=0011492314&partnerID=8YFLogxK
U2 - 10.1021/om00148a026
DO - 10.1021/om00148a026
M3 - Article
AN - SCOPUS:0011492314
VL - 6
SP - 1065
EP - 1073
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 5
ER -