Chromium compounds coordination number

SCN- is the thiocyanate ion). Consider the oxidation number of chromium to be +3 and the coordination number to be 6 in both compounds. Estimate... 

Among the compounds that form complexes with silver and other metals are benzene (represented as in 9) and cyclooctatetraene. When the metal involved has a coordination number >1, more than one donor molecule participates. In many cases, this extra electron density comes from CO groups, which in these eomplexes are called carbonyl groups. Thus, benzene-chromium tricarbonyl (10) is a stable compound. Three arrows are shown, since all three aromatic bonding orbitals contribute some electron density to the metal. Metallocenes (p. 53) may be considered a special case of this type of complex, although the bonding in metallocenes is much stronger. 

A coordination number of 7 does not seem likely for chromium (III) also, the infrared spectrum indicates that this compound contains uncoordinated hydroxyl groups. The similarity of the visible-ultraviolet absorption spectra of [Cr(HO-A)2] and [Cr(AcO-A)2] (above) is further evidence of the identical character of the donor groups in both compounds, and hence, hydroxyl groups appear to be uncoordinated in the former. We must seek an explanation not involving coordination of the hydroxyl oxygen to chromium (III). 

CN depends not only on the composition of a coordination compound, but also on the type of a- and n-bonds present in it. Chromium carbonyl-pyridine complexes are the classic example to illustrate the difficult task of determining unambiguously the coordination numbers. Only a-bonds are present in Cr(py)(CO)5 and CN = 6 (12). However, in the a, n-complex 13, as well as in 9, the coordination number is quite questionable (compare formulae 9 IT). 

Chromium ions at the surfaces of inorganic oxides are characterized by a wide variability of the oxidation state, coordination number, and local structure. Consequently, Cr-based materials are especially attractive as catalysts. Much is known about the catalytic activity of pure Cr203 for various reactions (469), including polymerization of alkenes (470-472), hydrogenation-dehydrogenation of hydrocarbons (473-481), reduction of NO and decomposition of N2O4 (482), and oxidation of organic compounds (483, 484). 

The very air-sensitive compounds [Mo(terpy)2] (purple) and [W(terpy)2] (green) have been described by a number of workers 44,174). The chromium compound may be prepared by the reaction of [Cr(CO)g] 44), [Cr(CN)g] 42,47), [Cr(CO)3(C6H6)] 47), or [Cr(bipy)3] 44) with two equivalents of terpy. The molybdenum 44,174) and tungsten 44) compounds have been prepared from [M(CO)g] in a similar manner. Electrochemical studies on [Mo(terpy)2] indicate three one-electron oxidations 8). Photosubstitution reactions of [M(CO)g] in the presence of limited amounts of terpy lead to the formation of [M(CO)4(terpy)] (M = Cr, Mo, or W) 205). It is unlikely that these compounds are seven-coordinate, and they may well provide examples of a bidentate terpy. [Mo(CO)3(terpy)] may be prepared by the reaction of terpy with [Mo(CO)3(mesitylene)], but attempts to prepare the other group VI complexes of this stoichiometry lead to the formation of [M(CO)4(terpy)] 205). 

Chromium complexes exist in a very wide range of formal oxidation states (-IV to +VI). The extremely low ones are stabilized by jr-acid ligands, notably carbon monoxide these are described in the article on organometallic compounds (see Chromium Organometallic Chemistry). The extensive coordination chemistry of Cr spans coordination numbers 3-7, but is dominated by octahedral complexes. Complexes of... 

Compound 10 has been used for the preparation of chromium silylene (silandiyl) complexes containing coordinatively (and presumably also electronically) unsaturated Si [23]. Not surprisingly, in this complex an additional phosphorus coordination to silicon is observed (c (Si-P) = 2.380(1) A), whereby silicon expands its coordination number from three to four. 

This is by far the most common coordination number. With certain ions six-coordinate complexes are predominant. For example, chromium(lll) and cobalt(lll) are almost exclusively octahedral in their complexes.It was this large series of octahedral Cr(III) and Co(III) complexes which led Werner to formulate his theories of coordination chemistry and which, with square planar platinum(II) complexes, formed the basis for almost all of the classic work on complex compounds. Before discussing the various isomeric possibilities for octahedral complexes, it is convenient to dispose of the few nonoctahedral geometries. 

Monomeric species M OR-tert)x have been characterized for titanium, vanadium, chromium, zirconium, and hafnium (x = 4) and for niobium and tantalum (x == 5). With chromium it was found that limiting Cr(III) to coordination number 4 in the dimeric Cr2(OBu )e caused instability and a remarkable facility toward valency disproportionation or oxidation to the stable quadricovalent Cr(OBu )4 (8, 9). In contrast, molybdenum formed a stable dimeric tri-tert-butoxide (Bu O)3Mo=Mo-(OBu )3 which is diamagnetic and presumably bound by a metal-metal triple bond (10, II). Yet another interesting feature of chromium is the synthesis of a stable diamagnetic nitrosyl Cr(NO) (OBu )3 in which the nitric oxide is believed to act as a three-electron donor with formation of a four-coordinated low spin chromium (II) compound (12). The insta-bihty of Cr2(OBu )e and the stability of both Cr(NO) (OBu )3 and Cr(OBu )4 must result from the steric effects of the tertiary butoxo groups since the less bulky normal alkoxo groups form very stable polymeric [Cr(OR)3]a. compounds in which the Cr(III) has its usual coordination number of 6 (octahedral). 

In the second short period and the first long period, the maximum coordination number is 6. SiFe and the very stable SFe are examples from the second short period, but only the fluoride ion is small enough to form stable 6-coordinated compounds in this period. In the first long period we have many more examples, such as the 6-coordi-nated complexes of chromium, iron, and cobalt. Neverthe-... 

Most metals can form some coordination compounds, but few form as many as trivalent cobalt. Others that do include trivalent chromium, and bi- and quadri-valent platinum. Trivalent chromium and quadrivalent platinum have the same coordination number and geometry as trivalent cobalt bivalent platinum has a coordination number of four with the groups around it arranged in a square. 

Manganese(II) has one electron in each of the d-like orbitals, and thus there is no reason for octahedral symmetry like in chromium(III) by ligand field stabilization. Thus, one can find a variety of compounds in which the coordination number of Mn(II) can acquire values from 4 to 7 (Reisfeld. et al., 1984b,c). 

Na[AuClJ, per mole of silver haHde. Coordination compounds are used as emulsion stabilizers, developers, and are formed with the weU-known thiosulfate fixers. Silver haHde diffusion transfer processes and silver image stabilization also make use of coordination phenomena. A number of copper and chromium azo dyes have found use in diffusion transfer systems developed by Polaroid (see Color photography, instant). Coordination compounds are also important in a number of commercial photothermography and electrophotography (qv) appHcations as weU as in the classic iron cyano blueprint images, a number of chromium systems, etc (32). 

Forms a number of coordination compounds (ammonia complex) with several metals adds to AgCl forming soluble complex [Ag(NH3)2]Cl forms tetraamine complex [Cu(NH3)4]S04 with CUSO4 and forms many hexaamine complexes with cobalt, chromium, palladium, platinum and other metals. 

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