Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 134, Issue 26, Pages 10864-10875Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja301547x
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Funding
- Austrian Fonds zur Forderung der wissenschaftlichen Forschung (FWF) [P-19338, P-21346]
- Fonds der Chemischen Industrie (FCI) [183191]
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Reduction of group 4 metallocene dichlorides with magnesium in the presence of cyclic disilylated stannylene or plumbylene phosphine adducts yielded the respective metallocene tetrylene phosphine complexes. Under the same conditions the use of the respective dimerized stannylene or plumbylene gave metallocene ditetrylene complexes. A computational analysis of these reactions revealed for all investigated compounds multiple-bonded character for the M-E(II) linkage, which can be rationalized in the case of the monotetrylene complex with the classical sigma-donor/pi-acceptor interaction. The strength of the M-E(II) bond increases descending group 4 and decreases going from Sn to its heavier congener Pb. The weakness of the Ti-E(II) bonds is caused by the significantly reduced ability of the titanium atom for d-p pi-back-bonding.
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