TY - JOUR
T1 - Übergangsmetall-methylen-komplexe. LVI. Organoruthenium-komplexe mit offenkettigen und carbocyclischen alkyliden-brücken
T2 - Synthese, konstitution, isomerie, protonierung und thermolytischer abbau
AU - Herrmann, Wolfgang A.
AU - Flöel, Martina
AU - Weber, Cornelia
AU - Hubbard, John L.
AU - Schäfer, Adolf
PY - 1985/5/14
Y1 - 1985/5/14
N2 - The eighteen new μ-alkylidene ruthenium complexes 5a-r and 5t are very easily and cleanly obtained along the diazoalkane or the hydrazone routes that involve treatment of the dinuclear, metal-metal doubly bonded precursor compound [(η5-C5H5)Ru(μ-NO)]2 (3) either with the diazoalkanes oxidizing agent (e.g., MnO2), with the respective hydrazones. Similarly, sulfur dioxide adds cleanly to the RuRu double bond of 3, thus giving the complex (μ-SO2)[(η5-C5H5)Ru(NO)]2 (5s). Regardless of the nature of the carbene bridge ligands, the dimetallacyclopropanes exhibit, in contrast to their iron analogues, exclusively terminal nitrosyl ligands. cis/trans-Isomerism with predominating amounts of the trans-isomers is observed for the derivatives that display unsymmetrically substituted carbene bridges. Treatment of the μ-methylene- and μ-ethylidene complexes (μ-CH2)[(η5-C5H5)Ru(NO)]2 (5a) and (μ-CHCH3)[(η5-C tetrafluoroboric acid or trifluoromethanesulfonic acid in diethyl ether yields, at ambient temperature, quantitatively the ionic complexes 6a,b and 7a,b, respectively, which were shown by 1H NMR spectroscopy to contain metal-metal bridging hydrogen functionalities. The reaction of hydrogen bromide with 5a under the same conditions gives the neutral bromo(methyl) complex 6d. This latter compound results from the isolable ionic intermediate of composition [(μ-CH2)(μ-H){(η5C5H5)Ru(NO)}2]+Br- (6c), which reaction stems from the nucleophilicity of the halide ion present in 6c.
AB - The eighteen new μ-alkylidene ruthenium complexes 5a-r and 5t are very easily and cleanly obtained along the diazoalkane or the hydrazone routes that involve treatment of the dinuclear, metal-metal doubly bonded precursor compound [(η5-C5H5)Ru(μ-NO)]2 (3) either with the diazoalkanes oxidizing agent (e.g., MnO2), with the respective hydrazones. Similarly, sulfur dioxide adds cleanly to the RuRu double bond of 3, thus giving the complex (μ-SO2)[(η5-C5H5)Ru(NO)]2 (5s). Regardless of the nature of the carbene bridge ligands, the dimetallacyclopropanes exhibit, in contrast to their iron analogues, exclusively terminal nitrosyl ligands. cis/trans-Isomerism with predominating amounts of the trans-isomers is observed for the derivatives that display unsymmetrically substituted carbene bridges. Treatment of the μ-methylene- and μ-ethylidene complexes (μ-CH2)[(η5-C5H5)Ru(NO)]2 (5a) and (μ-CHCH3)[(η5-C tetrafluoroboric acid or trifluoromethanesulfonic acid in diethyl ether yields, at ambient temperature, quantitatively the ionic complexes 6a,b and 7a,b, respectively, which were shown by 1H NMR spectroscopy to contain metal-metal bridging hydrogen functionalities. The reaction of hydrogen bromide with 5a under the same conditions gives the neutral bromo(methyl) complex 6d. This latter compound results from the isolable ionic intermediate of composition [(μ-CH2)(μ-H){(η5C5H5)Ru(NO)}2]+Br- (6c), which reaction stems from the nucleophilicity of the halide ion present in 6c.
UR - https://www.scopus.com/pages/publications/46549095232
U2 - 10.1016/0022-328X(85)80052-8
DO - 10.1016/0022-328X(85)80052-8
M3 - Artikel
AN - SCOPUS:46549095232
SN - 0022-328X
VL - 286
SP - 369
EP - 397
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 3
ER -