TY - JOUR
T1 - Syntheses, structures, and bonding of Cp 2M(ER) 2 compounds (Cp = C 5H 5; M = Ti, Zr; e = Ga, In; R = C 6H 3-2,6-(2,4,6-i-Pr 3C 6H 2) 2)
AU - Yang, Xiao Juan
AU - Wang, Yuzhong
AU - Quillian, Brandon
AU - Wei, Pingrong
AU - Chen, Zhongfang
AU - Schleyer, Paul V.R.
AU - Robinson, Gregory H.
PY - 2006/2/13
Y1 - 2006/2/13
N2 - Sodium or magnesium metal reduction of Cp 2MCl 2 (Cp = C 5H 5; M = Zr, Ti) with RECl 2 (E = Ga, In; R = C 6H 3-2,6-(2,4,6-i-Pr 3C 6H 2) 2) affords heteronuclear organometallic compounds, Cp 2M(ER) 2, with new types of group 4-group 13 M-E bonds (Zr-Ga (1), Ti-Ga (2), Zr-In (3), Ti-In (4)). These compounds have been characterized by elemental analyses, 1H and 13C NMR spectroscopy, and single-crystal X-ray diffraction analyses. The structures of 1-4 have V-shaped E-M-E trimetallic linkages with quite short M-E bonds (Zr-Ga, 2.6350(8) A°; Ti-Ga, 2.4921(7) A°; Zr-In, 2.7916(5) A°; Ti-In, 2.6685(8) A°). The transition metal (M = Zr, Ti) centers adopt a pseudo-tetrahedral coordination geometry, while the main group metal (E = Ga, In) atoms reside in a two-coordinate, almost linear environment. Density functional theory (DFT) computations on the model compounds Cp 2M(EPh) 2 (1Ph-4Ph) suggest significant π-back-bonding from the group 4 metals (Zr, Ti) to the group 13 metals (Ga, In) in these compounds.
AB - Sodium or magnesium metal reduction of Cp 2MCl 2 (Cp = C 5H 5; M = Zr, Ti) with RECl 2 (E = Ga, In; R = C 6H 3-2,6-(2,4,6-i-Pr 3C 6H 2) 2) affords heteronuclear organometallic compounds, Cp 2M(ER) 2, with new types of group 4-group 13 M-E bonds (Zr-Ga (1), Ti-Ga (2), Zr-In (3), Ti-In (4)). These compounds have been characterized by elemental analyses, 1H and 13C NMR spectroscopy, and single-crystal X-ray diffraction analyses. The structures of 1-4 have V-shaped E-M-E trimetallic linkages with quite short M-E bonds (Zr-Ga, 2.6350(8) A°; Ti-Ga, 2.4921(7) A°; Zr-In, 2.7916(5) A°; Ti-In, 2.6685(8) A°). The transition metal (M = Zr, Ti) centers adopt a pseudo-tetrahedral coordination geometry, while the main group metal (E = Ga, In) atoms reside in a two-coordinate, almost linear environment. Density functional theory (DFT) computations on the model compounds Cp 2M(EPh) 2 (1Ph-4Ph) suggest significant π-back-bonding from the group 4 metals (Zr, Ti) to the group 13 metals (Ga, In) in these compounds.
UR - http://www.scopus.com/inward/record.url?scp=33644503581&partnerID=8YFLogxK
U2 - 10.1021/om050825n
DO - 10.1021/om050825n
M3 - Article
AN - SCOPUS:33644503581
SN - 0276-7333
VL - 25
SP - 925
EP - 929
JO - Organometallics
JF - Organometallics
IS - 4
ER -