Hydrocarbon-bridged Metal Complexes. XXXIX. Chemistry of Pentacarbonyl-rhenium-acetylides

Article abstract of DOI:10.1016/S0022-328X(97)00119-8

As a by-product in the preparation of (OC)5Re-C<*>C-Re(CO)5 (1) from <(OC)5Re(μ-η¹:η²-C<*>CH)Re(CO)5>BF4 and K the new fluxional hydride-bridged cluster (OC)5Re-C<*>C-Re(CO)4 (2) is obtained. (OC)5Mn-C<*>C-Mn(CO)5 (4) is available from <(OC)5Mn(η¹:η²-C<*>CH)Mn(CO)5>BF4 (3) and K.Reaction of 1 with Me3O⁺BF4^- gives the ?,?-bridged complex <(OC)5Re(μ-η¹:η²-C<*>CMe)Re(CO)5>BF4 (5).The alkynyl complex (OC)5Re-C<*>C-SiMe3 (6) can be prepared by reaction of Na with 1-tosyl-2-trimethylsilyl-ethyne.The reaction of tosylethyne with Na affords (OC)5Re-C<*>CH (7) and (OC)5Re-C(H)=C(H)(tosyl) (9).Complex 7 is also formed by cleavage of the Me3Si group from 6. (OC)5ReOSO2CF3 reacts with Li(en)C<*>CH to give the chelate carbamoyl complex (OC)4Re<*>NH2CH2CH2NHC<*>O (8).Elimination of CO from (OC)5Re-C<*>CRe(CO)5 gives the tetrameric ?,?-acetylide-bridged cluster <(OC)5Re-C<*>C-Re(CO)4>2 (11).Similarly, C-Re(CO)4>2 (12) is formed from Me3Si-Re(CO)5.The structures of 2, 9, 11 and 12 were determined by X-ray diffraction.As by-products from the thermolysis of 1 and 7, 4*4H2O and <(OC)3ReOH>4*4(OC)5ReCOCH3 were obtained.Keywords: Pentacarbonylrhenium; Alkynediide; Alkynyl ligand