96412-33-8Relevant academic research and scientific papers
Synthesis, Reactivity, and Spectroscopic Studies of Some Tetranuclear OSmium Clusters. Structural Characterization of 3-NC(O)Me> (M=Au or Cu) and
Puga, Jose,Arce, Alejandro,Sanchez-Delgado, Roberto A.,Ascanio, Julian,Andriollo, Antida,et al.
, p. 913 - 924 (2007/10/02)
The interaction of (1) with (X=NO2, Cl, Br, or I) affords the species 3-NC(O)Me>> (2) (X=NO2), , and which were characterized by i.r. and 1H n.m.r. spectroscopy.The reaction of complex (1) with nitrite ion results in a novel interaction which involves oxygen transfer from the nitrite ion and conversion of a co-ordinated NCMe ligand into an amido group on the cluster surface.The anionic species (2) reacts with + to yield the neutral mixed-metal clusters 3-NC(O)Me>> which have been structurally characterized by single-crystal X-ray diffractometry.This shows that they possess a butterfly metal framework capped by the heterometallic fragment and μ3-bridged by the four-electron-donor amido group.Complexes (3) and (4) are isomorphous, monoclinic, with space group C2/c and Z=8:: (3), a=25.681(7), b=16.069(1), c=18.265(2) Angstroem, and β=90.90(1) deg; (4) a=25.318(6), b=15.964(5), c=18.347(7) Angstroem, and β=91.80(2) deg.Spectroscopic data suggest that compounds (6) and (7) also possess a butterfly metal framework with a bridging, three-electron-donor, halide ligand, while the anionic species (11) possesses a tetrahedral arrangement of metal atoms with a terminally co-ordinated iodide ligand, as shown by X-ray diffractometry: monoclinic, space group P21/a, Z=8, a=16.841(2), b=20.699(1), c=29.249(3), and β=90.91(2) deg.Protonation of (11) yields the neutral species , showing that facile reversible tetrahedral-butterfly interconversion is assisted by a change in co-ordination mode and electron donation of the I atom.The reaction of compound (11) with CF3SO3R (R=Me or Et) was monitored by 1H n.m.r. spectroscopy and the results explained in terms of the formation of alkyl iodide derivatives.
Transition-metal trihalomethyl complexes as cluster-building reagents: Preparation and X-ray crystal structure of [PPN][MnCo2(CO)9(μ3-CCO)]
Crespi, Ann M.,Went, Michael J.,Sunshine, Steven S.,Shriver, Duward F.
, p. 214 - 218 (2008/10/08)
A new mixed-metal ketenylidene complex, [PPN][MnCo2(CO)9(μ3-CCO)] (1) (PPN+ = bis(triphenylphosphine)nitrogen(1+)), has been prepared from trihalomethyl manganese complexes, Mn(CO)5(CX3) (X = Cl or Br), in combination with [PPN][Co(CO)4]. Attempts to extend this technique to other trihalomethyl complexes and metal carbonyl anions did not yield any new cluster products. Instead, these reactions were characterized by electron-transfer chemistry, which resulted in oxidation of the anions. Crystal data for 1: triclinic space group P1; a = 14.859 (4) A?, b = 9.209 (1) A?, c = 16.701 (3) A?, a = 90.08 (2)°, β = 102.79 (2)°, γ = 89.99 (2)° Z = 2. Protonation of 1 leads to the new mixed-metal methylidyne MnCo2(CO)10(μ3-CH) (2).
Pentadienyl-metal-phosphine chemistry. 16. Reaction chemistry of (η3-2,4-dimethylpentadienyl)Rh(PEt3)2 and (η3-2,4-dimethylpentadienyl)Rh(PMe3)2
Bleeke, John R.,Donaldson, Andrew J.
, p. 1588 - 1596 (2008/10/08)
The reactions of (η3-2,4-dimethylpentadienyl)Rh(PEt3)2 (1) and (η3-2,4-dimethylpentadienyl)Rh(PMe3)2 (2) with CH3+O3SCF3- produce (η5-2,4-dimethylpentadienyl)Rh(PEt3) 2(Me)+O3SCF3- (3) and (η5-2,4-dimethylpentadienyl)Rh(PMe3) 2(Me)+O3SCF3- (4), respectively. The solid-state structure of 3 has been determined by single-crystal X-ray diffraction. The complex crystallizes in the monoclinic space group P21/c with a = 11.310 (2) A?, b = 13.507 (7) A?, c = 18.226 (3) A?, β = 95.97 (2)°, V = 2769 (3) A?3, and Z = 4. The coordination geometry of 3 is pseudooctahedral, with C(1), C(3), and C(5) of the 2,4-dimethylpentadienyl ligand and P(1), P(2), and C(8) (methyl carbon) occupying the six coordination sites. One of the phosphine ligands resides under the open mouth of the 2,4-dimethylpentadienyl ligand, while the other phosphine and the methyl group occupy the coordination sites under the edges of the 2,4-dimethylpentadienyl ligand. Upon heating in solution, the 2,4-dimethylpentadienyl ligand in 3 rotates with respect to the RhP2(Me) framework, exchanging the two phosphines, as well as the two ends of the 2,4-dimethylpentadienyl ligand. The energy of activation (ΔG?) for this dynamic process, derived from variable-temperature NMR studies, is 17.0 ± 0.7 kcal/mol. Treatment of 3 and 4 with (Ph3P)2N+Cl- produces (η3-2,4-dimethylpentadienyl)Rh(PEt3) 2(Me)(Cl) (5) and (η3-2,4-dimethylpentadienyl)Rh(PMe3) 2(Me)(Cl) (6), respectively. Compound 5 crystallizes in the monoclinic space group P21/c with a = 12.962 (3) A?, b = 8.236 (2) A?, c = 22.758 (6) A?, β= 94.19 (2)°, V = 2423 (2) A?3, and Z = 4. The coordination geometry of 5 is pseudooctahedral with C(1), C(3) (2,4-dimethylpentadienyl group), P(1), P(2), C(8) (methyl carbon), and Cl occupying the six coordination sites. The phosphines are trans to the 2,4-dimethylpentadienyl group, while the methyl and chloro ligands reside trans to one another. The η3-2,4-dimethylpentadienyl ligand has a syn geometry and is sickle-shaped. In solution, 5 undergoes a dynamic process involving isomerization of the 2,4-dimethylpentadienyl ligand from η3 to η1 coordination (ΔG? = 13.0 ± 0.5 kcal/mol). Treatment of 5 with 2 equiv of PMe3 produces 6 quantitatively. Treatment of 1 with HBF4·OEt2 yields (η4-2,4-dimethylpentadiene)Rh(PEt3)2 +BF4- (7), which reacts in situ with benzene and durene to release 2,4-dimethylpentadiene and produce (η6-benzene)Rh(PEt3)2+BF 4- (8) and (η6-durene)Rh(PEt3)2+BF 4- (9), respectively. Compound 9 crystallizes in the monoclinic space group P21/n with a = 8.349 (2) A?, b = 10.843 (8) A?, c = 29.535 (9) A?, β= 91.96 (2)°, V = 2672 (3) A?3, and Z = 4. In the solid state, the durene ring of 9 is nonplanar: the two unsubstituted durene ring carbon atoms are displaced out of the plane of the four methyl-substituted ring carbon atoms toward the rhodium center. Treatment of 2 with HBF4·OEt2 yields an equilibrium mixture of (η5-2,4-dimethylpentadienyl)Rh(PMe3) 2(H)+BF4- (10) and (η4-2,4-dimethylpentadiene)Rh(PMe3)2 +BF4- (11). This mixture reacts with benzene and durene to produce (η6-benzene)Rh(PMe3)2+BF 4- (12) and (η6-durene)Rh(PMe3)2+BF 4- (13), respectively.
