New silane-induced CO activation in [({eta}{sup 5}-H{sub 3}CC{sub 5}H{sub 4})Mn(CO){sub 2}{lg_bullet}THF]: Formation of the cyclic bis({mu}-carbyne) complex ({eta}{sup 5}-H{sub 3}CC{sub 5}H{sub 4})(CO)Mn({mu}-COSiH(t-Bu){sub 2}){sub 2}Mn(CO)({eta}{sup 5}-H{sub 3}CC{sub 5}H{sub 4}) and the CC-coupling reaction of the siloxy-carbyne ligands
- Technische Universitaet Muncheen (Germany)
The labile complex [({eta}{sup 5}-H{sub 3}CC{sub 5}H{sub 4})Mn(CO){sub 2}{lg_bullet}THF] (6) is generated by photolysis of ({eta}{sup 5}-H{sub 3}CC{sub 5}H{sub 4})Mn(CO){sub 3} (5) and subjected to oxidative addition reactions with various silanes. With (t-Bu){sub 2}SiHCl (7) the cyclic bis({mu}-carbyne) complex ({eta}{sup 5}-H{sub 3}CC{sub 5}H{sub 4})(CO)Mn({mu}-COSiH(t-Bu){sub 2}){sub 2}Mn(CO)({eta}{sup 5}H{sub 4}) (8) is formed in 15% yield. A systematic investigation of the product distribution in these reactions shows that the formation of bis({mu}-carbyne) complexes versus silylmetal hydrides is a strong function of the substituents at the silane. A single-crystal X-ray structure determination of 8 shows a cyclic four-membered ring structure with a bond distance Mn-C15 (carbyne C) of 1.857 (2) A. The metallacycle is folded along the Mn-Mn bond (2.565 (1) A) which is in accordance with an all-trans geometry of the ring substituents. This ring geometry opens up a reaction pathway for 1,3-cis elimination reaction of bis(siloxy)ethyne [(t-Bu){sub 2}HSiOC{triple_bond}]{sub 2} (9) via a CC-coupling reaction of both carbyne units as C2/c, {alpha} = 31.283 (3) A, B = 8.350 (1) A, c = 16.312 (2) A, {Beta} =126.63 (1){degrees}, Z = 8. 28 refs., 3 figs., 6 tabs.
- OSTI ID:
- 412000
- Journal Information:
- Organometallics, Journal Name: Organometallics Journal Issue: 11 Vol. 11; ISSN ORGND7; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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