“…Complexes 29 (M = W) also react with excess CH2X2 in hot toluene, resulting in the formation of paramagnetic diazoalkane comlexes mer,trans-[WX3(NN=CRR0(PMe2Ph)2] (X = Br, I). 129 The bonding parameters associated with the diazoalkane ligand in this W(V) complex (X = Br, R = Me, R' = Ph) are quite similar to those in the W(IV) complexes.…”
Section: B C-n Bond Formation At Coordinated N2 Via Hydrazido(2-) or ...mentioning
“…Complexes 29 (M = W) also react with excess CH2X2 in hot toluene, resulting in the formation of paramagnetic diazoalkane comlexes mer,trans-[WX3(NN=CRR0(PMe2Ph)2] (X = Br, I). 129 The bonding parameters associated with the diazoalkane ligand in this W(V) complex (X = Br, R = Me, R' = Ph) are quite similar to those in the W(IV) complexes.…”
Section: B C-n Bond Formation At Coordinated N2 Via Hydrazido(2-) or ...mentioning
“…Diazoalkanes are important reagents in both cyclopropanation reactions – and for the generation of metallacarbene complexes. ,– In addition to their role as carbene sources, the coordination chemistry of diazoalkanes is equally rich, ,,, displaying a variety of coordination modes, as shown in Chart . When bound to a single metal center two coordination modes have commonly been observed, involving either η 1 , end-on coordination (type I ), – which can assume a number of valence-bond formulations and associated geometries, or the η 2 -NN side-on 1 coordination (type II ). ,– In addition, three other coordination modes can also be envisioned, although they have yet to be observed: an η 2 -NC side-on coordination (type III ), a four-membered “MCNN” metallacycle (type IV ), and a η 1 -C-bound coordination (type V ). In binuclear complexes containing two metal centers, diazoalkane coordination at either one of the metals, as illustrated above in structures I − V , can again occur; however, additional modes are also possible in which the diazoalkane bridges the pair of metals.…”
The substituted diazoalkanesethyl diazoacetate (EDA), diethyl diazomalonate (DEDM), and trimethylsilyl diazomethane (TMSDM)react readily with the methylene-bridged tricarbonyl species [RhM(CO)3(μ-CH2)(dppm)2][CF3SO3] (M = Os (5), Ru (6); dppm = μ-Ph2PCH2PPh2) to produce the corresponding substituted olefin (through loss of N2 and subsequent coupling of the diazoalkane-generated alkylidene fragment and the methylene unit), the known tetracarbonyl species [RhM(CO)4(dppm)2][CF3SO3] (M = Os (1), Ru (2)), and uncharacterized decomposition products. In the reaction of 5 with EDA at −20 °C the intermediate olefin adduct, [RhOs(CO)3(η2-CH2-CHR)(dppm)2][CF3SO3] (7; R = CO2Et) is observed, which decomposes with release of the olefin upon warming. The methylene-bridged tetracarbonyl species [RhM(CO)4(μ-CH2)(dppm)2][CF3SO3] (M = Os(3), Ru (4)) also react with these diazoalkanes to yield the same products, only at a much slower rate. Attempts to generate the alkylidene-bridged products, analogous to 3 and 4, by reaction of 1 or 2 with EDA, DEDM, and TMSDM accompanied by loss of N2 instead gave complexes containing the diazoalkane unit. In the reaction with EDA condensation of this unit with a carbonyl ligand occurs accompanied by migration of the diazoalkane hydrogen to the carbonyl oxygen, yielding [RhM(CO)3(μ-η1:η1-N2C(COH)CO2Et)(dppm)2][CF3SO3] (M = Os (8), Ru (9)). The new diazoalkane-like group bridges the metals via the terminal nitrogen, while also binding to the group 8 metal via the enol carbon that originated from a carbonyl group. In the related reaction involving DEDM, substitution of a carbonyl yields [RhM(CO)3(μ-η1:η1-N2C(CO2Et)2)(dppm)2][CF3SO3] (M = Os (10), Ru (11)), in which the intact diazoalkane ligand again bridges via the terminal nitrogen. However, in this case one of the ester carbonyls binds to the group 8 metal, replacing the carbonyl group that was displaced. Although the RhRu compound 2 does not react with TMSDM, the analogous RhOs compound (1) does react, yielding [RhOs(CO)3(η1-Ν2CHSiMe3)(dppm)2][CF3SO3]] (12), in which the TMSDM ligand binds terminally on Os opposite the Rh−Os bond.
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