Carbonyl complexes of niobium

No cationic carbonyl complexes of niobium and tantalum have been reported. 

The monomeric carbonyl complexes of d M1 isolated so far are mainly the seven-coordinated [MX(CO)2(dmpe)2] compounds (M = Nb, X = Cl, Br, N3 697 M = Ta, X = H, Cl, Br, CN, Me, Et, Pr ) (53) has been obtained by reduction of [TaCl2(dmpe)2] with one equivalent of sodium naphthalenide under CO the other tantalum derivatives were generally prepared by oxidative additions to [Ta(CO)2(dmpe)2] formed in situ by reduction of (53 Scheme 10). The niobium analogs were formed by reductive carbonylation of [NbCU(dmpe)2].698... 

A recent review gives a chronological survey of the syntheses and characterizations of homoleptic mononuclear metal-carbonyl (see Carbonyl Complexes of the Transition Metals) anions. [M(CO)6] is a key precursor to niobium and tantalum carbonyls. More reliable synthesis of [Ta(CO)6] ... 

Carbonyl Complexes of the Transition Metals Mechanisms of Reaction of Organometallic Complexes Niobium Tantalum Organometallic Chemistry. 

Many carbonyl and carbonyl metallate complexes of the second and third row, in low oxidation states, are basic in nature and, for this reason, adequate intermediates for the formation of metal— metal bonds of a donor-acceptor nature. Furthermore, the structural similarity and isolobal relationship between the proton and group 11 cations has lead to the synthesis of a high number of cluster complexes with silver—metal bonds.1534"1535 Thus, silver(I) binds to ruthenium,15 1556 osmium,1557-1560 rhodium,1561,1562 iron,1563-1572 cobalt,1573 chromium, molybdenum, or tungsten,1574-1576 rhe-nium, niobium or tantalum, or nickel. Some examples are shown in Figure 17. 

R. R.Schrock, The Reaction of Niobium and Tantalum Neopentylidene Complexes with the Carbonyl Function, J. Am. Chem. Soc. 98, 5399-5400 (1976). 

A related reaction is shown for the molybdenum-niobium complex (equation 9). As described in a review by Horowitz and Shriver on bridging carbonyl ligands, this complex is a rare example of a structure containing terminal, bridging, and r-bridging CO ligands. All such complexes, of necessity, include metal-metal bonding. 

No derivative in which niobium or tantalum displays an oxidation state of —II has been reported so far, while carbonyl complexes derived from [M(CO)s] represent the only coordination compounds for these metals in oxidation state —III. 

The Wittig-type olefination of carbonyl compounds is one of the characteristic reactions of carbene complexes. High-valent carbene complexes of early transition metals show ylide-like reactivity to vards carbonyl compounds. In 1976, Schrock first demonstrated that niobium and tantalum neopentylidene complexes 1 and 2, the typical nucleophilic Schrock-type carbene complexes, olefinate various carbonyl compounds including carboxylic acid derivatives [4]. 

Vanadium, Niobium, and Tantalum.—High-pressure carbonylation of [CpNbCy in the presence of Na-Cu-Al affords high yields ca. 90%) of [CpNb(CO)4], and the preparation can be carried out on a large scale ca. 35 g) irradiation of this product in solution in THF affords [CpNb(CO)3(THF)], which is a useful intermediate for the preparation of complexes of the type [CpNb(CO)3L] e.g., reactions with CO and to afford a labelled tetracarbonyl. A study of... 

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