Molybdenum–tin and molybdenum–copper complexes derived from the molybdenum tricarbonyl anions, LMo(CO)₃⁻ (where L = HBpz₃ or HBpz″₃; pz = pyrazolyl, N₂C₃H₃; and pz″ = 3,5-dimethylpyrazolyl, N₂C₅H₇)

Organometallic Probe for the Electronics of Base‐Stabilized Group 11 Metal Cations

“…One characteristict rait of heterobimetallics in which the anionic bonding partner bears CO ligandsi st he formation of close contacts between the incoming cationic fragment and one or more of these COs (Figure 2a). [26,27] These interactions are found in each of the nine isolated compounds, manifest in moderately short OCÀ . Md istances, slight deviations from the ideal linearityo ft he MnÀCÀOa ngle, and elongated MnÀCO bondsf or the affected CO ligands (see Ta bleS2i nt he Supporting Information).…”

“…Both gold and silver phosphines have shown the capacity to form these structures, [25] and recently Mankad and co-workers published an array of bimetallicc ompounds containing NHC-stabilized copper, [26] thereby supplementing the existing literature on amine-and phosphine-stabilized copperh eterobimetallics. [27] Calculations on anion 1 indicate that most of the negative chargei sl ocalized on the manganese atoms (À0.69, NaturalP opulation Analysis), [20b] making these sites potentially nucleophilic. In Mankad's adduct of [IPr-Cu] + (IPr = 1,3-(diisopropyl)imidazol-2-ylidene) and [Mn(CO) 5 ] À (Figure 2a), the MnÀCu bond (2.415(1)) [26b] is shorter than the average MnÀCu distances in 1·Cu PCy3 (2.692 ), 1·Cu ITol (2.686 ), and 1·Cu CAAC (2.772 ); however,e ach of the observed MnÀCu distances in the structures in Figure 1f all either at or below the sum of the covalent radii for coppera nd manganese (2.71 ), as determined by Cordero et al, [28] with the exception of one of the MnÀCu bonds in 1·Cu CAAC ,w hich is am odest 4% greatert han the sum of the radii.…”

“…Figure 2. a) Geometries exhibited by compoundsconstructed of metalmetal interactions, [26,27] b) geometries exhibited by compoundsc omposedo f p!Minteractions, [13] and c) comparison of the two structural groups observed for the 1·M L complexesand their respectivec lassification.…”

Transition metal-substituted paraffins: synthesis and properties of some μ-saturated heterobimetallic complexes containing Mo and W or Fe and the crystal structures of [(η5-C5H5)(CO)3W(CH2)3Mo(CO)2(PPh3)(η5-C5H5)] and [(η5-C5H5)(CO)2(PPh3)Mo(CH2)3Fe(CO)2(η5-C5H5)]

“…Table 4 Selected bond lengths and angles ( A A,°) for 3a and 7a (1) 2.022(4) W(1)-Cg (2) 1.997 (3) Mo(1)-Cg (3) 2.0164 (16) Fe(1)-Cg (4) 1.7206 (15) Basal Y Mo(1)-C (17) 1.960 (7) W(1)-C (14) 1.988 (8) Mo(1)-C(1)…”

“…They have been proposed to be good models for the Fischer-Tropsch processes [5]. Bimetallic compounds with direct metal-metal bonds are reported to be commonly synthesized by a metathesis of a halide ligand, usually on a group 4 metal, with an organometallic anion, such as [Cp(CO) 2 M] À (M ¼ Fe, Ru, Cp ¼ (g 5 -C 5 H 5 )) [6][7][8][9][10] or [(CO) 4 M] À (M ¼ Co, Rh) [6,7,[11][12][13][14][15]. The same procedure has been used to prepare heterobimetallic lanthanide [11] and group 6 and 9 complexes [12,13].…”