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(We tested that the same exchange occured in our experimental conditions.)
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70450221628
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...O hydrogen bonds from tmeda methyl and methylene and even from the olefin.
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...O hydrogen bonds from tmeda methyl and methylene and even from the olefin.
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63
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0011593001
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For the bond lengths, the average deviation is 0.04 Å, while the greatest deviation is 0.09 Å and involves the Pt-N bond length cis to the olefin in 1b. For the bond angles, the average deviation is 1°, while the maximum deviation is 3.8° and it involves one CH3-Ntrans-Pt bond angle in 1b. The computed olefins are symmetrically bound to the metal centre, as experimentally observed. Upon coordination, the C=C bond undergoes a lengthening (by 0.06 Å in 1a and 0.09 Å in 1b, The α angle, which is a measure of the bending-back of olefin substituents, is close to 32° in both complexes and similar to the experimental value found in Zeise's anion (for the definition of α angle see J.K. Stalick, J.A. Ibers, J. Am. Chem. Soc. 92 (1970) 5333 and J.S. Ricci, J.A. Ibers, J. Am. Chem. Soc. 93 (1971) 2391
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trans-Pt bond angle in 1b. The computed olefins are symmetrically bound to the metal centre, as experimentally observed. Upon coordination, the C=C bond undergoes a lengthening (by 0.06 Å in 1a and 0.09 Å in 1b). The α angle, which is a measure of the bending-back of olefin substituents, is close to 32° in both complexes and similar to the experimental value found in Zeise's anion (for the definition of α angle see J.K. Stalick, J.A. Ibers, J. Am. Chem. Soc. 92 (1970) 5333 and J.S. Ricci, J.A. Ibers, J. Am. Chem. Soc. 93 (1971) 2391).
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