Publisher Summary Metal carbonyls, which were among the earliest discovered organometallic compounds, continue to play a central role in organometallic chemistry. Carbonyl basicity is found for C-bridging CO ligands in metal–metal bonded compounds, CO ligands in anionic metal carbonyls, or CO ligands in donor-substituted metal carbonyls. The interaction of protons with mononuclear metal carbonyls readily occurs at the metal center rather than the CO oxygen; no stable or transient MCO–H species appear to have been observed. The chemical and structural characterization of molecular compounds containing π–CO is of great interest, because the π–CO is implicated as a precursor to the cleavage of CO on metal surfaces, such as those employed in Fischer–Tropsch catalysis. In view of these large physical changes, it perhaps is not surprising that C and O bonding also engenders large changes in CO reactivity. Carbon monoxide insertion into a metal–alkyl bond is a fundamental reaction in organometallic chemistry as well as an important step in the commercial production of oxygen-containing organics, such as aldehydes and acetic acid.

C- and O-Bonded Metal Carbonyls: Formation, Structures, and Reactions

The structural and spectroscopic similarities between homogeneous and heterogeneous [CuI(CO)n]+A- (n = 1−3; A- = [AsF6]- or zeolite anion Z-) carbonyls are evidenced and discussed. While [CuI(CO)2]+ and [CuI(CO)3]+ have linear and planar structures in [CuI(CO)n]+[AsF6]- solid compounds, they are bent in the zeolite channels. The [AsF6]- anion has a base strength lower than that of the zeolite anion; consequently, the [CuI(CO)n]+ moieties have a more positive character in the solid compounds than in the intrazeolitic ones. The CuI−framework distance is influenced by the formation of the [CuI(CO)n]+ complexes:  this is demonstrated by both EXAFS and IR results concerning the effect of CO complexation on the CuI−framework distance and on the CuI-sensitive skeletal modes, respectively. The role of basic ligands in increasing the π-character of the Cu−CO bond (with simultaneous decrease of the electrostatic and σ contributions) has been studied on [CuI(CO)n(NH3)]+Z- (n = 1, 2) and [CuI(CO)(H2O)n]+Z- (n = 1, 2)...

Mono-, Di-, and Tricarbonylic Species in Copper(I)-Exchanged Zeolite ZSM-5: Comparison with Homogeneous Copper(I) Carbonylic Structures

Structure and Bonding in Copper(I) Carbonyl and Cyanide Complexes

Exposing crystalline CuAsF6 to < 1 atm CO produces the homoleptic copper carbonyl cations [Cu(CO)]+, [Cu(CO)2]+, and [Cu(CO)3]+. These complexes were characterized by IR and Raman spectroscopy and by tensimetric titrations. The IR and Raman data are consistent with a two-coordinate, linear structure for the [Cu(CO)2]+ cation and with a three-coordinate, trigonal-planar structure for the [Cu(CO)3]+ ion. The compounds [Cu(CO)2][AsF6] and [Cu(CO)3][AsF6] represent the first examples of isolable polycarbonyls of Cu(I).

[Cu(CO)(n)()](+) Complex Ions in the Solid State (n = 1, 2, 3).

Seven new manganese(II, III, IV) pyridinecarboxylate compounds (Et4N)[MnCl2(pic)(2)] (1, Hpic = picolinic acid) [MnCl(Pic)(2)(H2O)].H2O (2), [MnCl(pic)(H2O)2](n) (3), [Mn(Pic)(2)](n) (4), [MnCl(pic ...

Synthesis, Structural Characterizations and Magnetic Properties of a Series of Mono-, Di- and Polynuclear Manganese Pyridinecarboxylate Compounds

Chloride-Induced Assembly of Manganese(II) Complexes Having Oligomeric and Chain Structures

Cristallisation dans le groupe C2/c avec a=20,630, b=5,004 et c=13,410 A, β=97,42°, Z=8. Affinement jusqu'a R=0,045. Coordination tetraedrique autour des atomes Cu. La structure generale consiste en chaines infinies de cycles a 8 chainons joints par des gorupes de trois atomes Cu−O−S

Preparation of copper(I) carbonyl complexes derived from sulfonic acids. Crystal structure of carbonylcopper ethanesulfonate (Cu(CO)C2H5SO3)

Preparation of copper(I) carbonyl complexes derived from sulfonic acids: crystal structure of Cu(CO)C2H5SO3

1) C 6 H 16 B 10 O cristallise dans C2/c avec a=21,702, b=8,662, c=13,610 A, β=102,11 o , Z=8; affinement jusqu'a R=0,056. 2) C 5 H 14 B 10 O cristallise dans Pbca avec a=22,822, b=10,797, c=9,280 A, Z=8; affinement jusqu'a R=0,067

http://journals.iucr.org/c/issues/1990/04/00/gr0029/gr0029.pdf

Structures of two carbon-to-boron bridged o-carboranes

The synthesis, structure, and dynamic behavior of [W(CPhCHCMe2)Br2(CO)2L], 2, are reported. A structural comparison with [W(CPhCHCHMe)Br2(CO)2L], 1, is made. The introduction of an additional methyl substituent at the vinyl group in 2 causes a significant lengthening of the metal-vinyl bond. Simple electronic considerations suggest that the weakness of the metal-vinyl interaction may be explained by the absence of π-backbonding. The presence of an additional methyl substituent in the vinylcarbene ligand also affects the reactivity of complex 2.

Structure and Reactivity of the Tungsten Vinylcarbene Complexes [W(=CPh-CH=CRMe)Br2(CO)2L] (R = H, Me; L = 4-Pico-Line). Is the Vinyl Group Acting as a Pure σ-Donor Ligand?

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