TY - JOUR
T1 - Reactions of monocyclopentadienyl complexes of molybdenum and tungsten with derivatives of phenols and pentafluorobenzeneselenol
AU - Davidson, Jack L.
AU - Holz, Birgit
AU - Leverd, Pascal C.
AU - Lindsell, W. Edward
AU - Simpson, Nigel J.
PY - 1994
Y1 - 1994
N2 - Reactions of [WI3(CO)2(Cp)] (cp = ?5-C5H5) with thallium salts Tl(OR) (R = aryl) in tetrahydrofuran did not produce simple substitution products but afforded reduced species [W(OC6F5)(CO)3(Cp)] 2, oxidised species [W(OC6H4Me-p)6] or the thallium tritungsten derivative [Tl{W(CO)3(cp)}3] (when R = C6H3Pri22,6). Complex 2 is a rare example of a derivative of type [WX(CO)3(Cp)] in which X is an oxygen-bonded ligand. Photolysis of [{Mo(CO)3(cp)}2] with Se2(C6F5)2 in toluene yields [Mo(SeC6F5)(CO)3(Cp)] 8a, and the thermal reaction of [MoCl(CO)3(Cp)] with two equivalents of Tl(SeC6F5) in diethyl ether gives the thallium complex Tl[Mo(SeC6F5)2(CO)2(Cp)] 9, via complex 8a isolated as a by-product. Reaction of [WBr3(CO)2(Cp)] with three equivalents of Tl(SeC6F5) produces [W(SeC6F5)3(CO)(Cp)] 12, with [W(SeC6F5)(CO)3(Cp)] 8b as a by-product, and further reaction of 12 with Tl(SeC6F5) forms [TlW(SeC6F5)4(Cp)] 11b. Variable-temperature 19F NMR studies show that complexes 9, 11b and 12 are fluxional and show hindered motion of the C6F5 rings. In complexes 9 and 11b, thallium(I) is co-ordinated by the selenolate ligands of the organometallic anion and coupling between 103/105Tl and 19F ortho-fluorine nuclei is observed in the 19FNMR spectra. Complex 12 comprises two conformers in equilibrium which are detected by NMR studies at low temperature. Comparisons are drawn between properties of the new selenium complexes and related sulfur derivatives.
AB - Reactions of [WI3(CO)2(Cp)] (cp = ?5-C5H5) with thallium salts Tl(OR) (R = aryl) in tetrahydrofuran did not produce simple substitution products but afforded reduced species [W(OC6F5)(CO)3(Cp)] 2, oxidised species [W(OC6H4Me-p)6] or the thallium tritungsten derivative [Tl{W(CO)3(cp)}3] (when R = C6H3Pri22,6). Complex 2 is a rare example of a derivative of type [WX(CO)3(Cp)] in which X is an oxygen-bonded ligand. Photolysis of [{Mo(CO)3(cp)}2] with Se2(C6F5)2 in toluene yields [Mo(SeC6F5)(CO)3(Cp)] 8a, and the thermal reaction of [MoCl(CO)3(Cp)] with two equivalents of Tl(SeC6F5) in diethyl ether gives the thallium complex Tl[Mo(SeC6F5)2(CO)2(Cp)] 9, via complex 8a isolated as a by-product. Reaction of [WBr3(CO)2(Cp)] with three equivalents of Tl(SeC6F5) produces [W(SeC6F5)3(CO)(Cp)] 12, with [W(SeC6F5)(CO)3(Cp)] 8b as a by-product, and further reaction of 12 with Tl(SeC6F5) forms [TlW(SeC6F5)4(Cp)] 11b. Variable-temperature 19F NMR studies show that complexes 9, 11b and 12 are fluxional and show hindered motion of the C6F5 rings. In complexes 9 and 11b, thallium(I) is co-ordinated by the selenolate ligands of the organometallic anion and coupling between 103/105Tl and 19F ortho-fluorine nuclei is observed in the 19FNMR spectra. Complex 12 comprises two conformers in equilibrium which are detected by NMR studies at low temperature. Comparisons are drawn between properties of the new selenium complexes and related sulfur derivatives.
UR - http://www.scopus.com/inward/record.url?scp=37049080186&partnerID=8YFLogxK
U2 - 10.1039/DT9940003527
DO - 10.1039/DT9940003527
M3 - Article
SN - 1472-7773
SP - 3527
EP - 3532
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 24
ER -