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• W1965756312 abstract "The synthesis and photochemistry of a series of new rhodium complexes of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, (CH2CHSiMe2)2O, and its disilazane analogue (CH2CHSiMe2)2NH are reported. The divinyldisiloxane or divinyldisilazane ligands in (η5-C5R5)Rh[η4-(CH2CHSiMe2)2X] (R = H, Me; X = O, NH; type 1 complexes) are coordinated through the vinyl groups as for a diene. The structure of (η5-C5Me5)Rh[η4-(CH2CHSiMe2)2O] was established crystallographically. The two coordinated double bonds are arranged with their Si substitutents in a cis orientation with respect to the metal. The strain in the structure is suggested by the scissor geometry of the vinyl CC bonds relative to the C5 plane of the ring, combined with unequal Rh-C and CC bond lengths. Photolysis of (η5-C5R5)Rh(C2H4)2 (R = H, Me) in the presence of (CH2CHSiMe2)2X (X = O, NH) results in the formation of the complexes of type 1, together with an isomer in which the substituents on the coordinated CC bonds are oriented trans at rhodium (2) and species containing two dangling divinyldisiloxane ligands, (η5-C5R5)Rh[η2-(CH2CHSiMe2)2X]2, in both cis and trans configurations. Direct irradiation of species of type 1 converts them to the photoisomer 2. The 16-electron intermediate with one η2-divinyldisiloxane ligand may be trapped by addition of CH2CHSiMe3 or excess (CH2CHSiMe2)2X (X = O, NH). The isomerization of type 2 species to type 1 species proceeds by first-order kinetics. For trans-(η5-C5H5)Rh[η4-(CH2CHSiMe2)2O] (2a) the values of ΔH⧧ and ΔS⧧ are 114 ± 1 kJ mol-1 and 41 ± 4 J mol-1 K-1, consistent with rate-determining dissociation of one double bond. Replacement of C5H5 by C5Me5 increases H⧧ by 9 ± 2 kJ mol-1. The assignment of the photoisomers 2 as the trans species is supported by further observations that (i) a mixture of 1 and 2 can be synthesized by hydrolysis of chlorovinylsilane precursors (η5-C5H5)Rh(η2-CH2CHSiMe2Cl)2, a method which generates the Si−O−Si linkage in situ, (ii) the conformationally locked species with a cyclic trivinyltrimethyltrisiloxane ligand, (η5-C5H5)Rh[η4-(CH2CHSi(Me)O)3], does not undergo photoisomerization, and (iii) the species with the Si−O−Si linkage replaced by a C−O−Si linkage (η5-C5H5)Rh[η4-(CH2CMe)CH2OSiMe2(CHCH2)] also fails to undergo photoisomerization. These complexes represent the first examples of adoption of a trans configuration at a metal by η4-divinyldisiloxane ligands and the first examples of this type of isomerization." @default.
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• W1965756312 title "Synthesis and Photoisomerization of Divinyltetramethyldisiloxane and Divinyltetramethyldisilazane Complexes of (η⁵-C₅R₅)Rh (R = H, Me). Crystal and Molecular Structure of (η⁵-C₅Me₅)Rh[η⁴-(CH₂CH)Me₂SiOSiMe₂(CHCH₂)]" @default.
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• W1965756312 doi "https://doi.org/10.1021/om950826n" @default.
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