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The trinuclear derivative Fe(3)(C(8)H(8))(3) was synthesized in 2009 by Lavallo and Grubbs via the reaction of Fe(C(8)H(8))(2) with a bulky heterocyclic carbene. This fascinating structure is the first example of a derivative of the well-known Fe(3)(CO)(12) in which all 12 carbonyl groups have been replaced by hydrocarbon ligands. The density functional theory predicts a structure having a central Fe(3) equilateral triangle with ∼2.9 A Fe-Fe single bonded edges bridged by η(5),η(3)-C(8)H(8) ligands. This structure is close to the experimental structure, determined by X-ray crystallography. The related hypoelectronic M(3)(C(8)H(8))(3) derivatives (M = Cr, V, Ti) are predicted to have central scalene M(3) triangles with edge lengths and Wiberg bond indices (WBIs) corresponding to one formal single M-M bond, one formal double M═M bond, and one formal triple M≡M bond. For Mn(3)(C(8)H(8))(3), both a doublet structure with one Mn═Mn double bond and two Mn-Mn single bonds in the Mn(3) triangle, and a quartet structure with two Mn═Mn double bonds and one Mn-Mn single bond are predicted. The hyperelectronic derivatives M(3)(C(8)H(8))(3) have weaker direct M-M interactions in their M(3) triangles, as indicated by both the M-M distances and the WBIs. Thus, Ni(3)(C(8)H(8))(3) has bis(trihapto) η(3),η(3)-C(8)H(8) ligands bridging the edges of a central approximately equilateral Ni(3) triangle with long Ni···Ni distances of ∼3.7 A. The WBIs indicate very little direct Ni-Ni bonding in this Ni(3) triangle and thus a local nickel environment in the singlet Ni(3)(C(8)H(8))(3) similar to that observed for diallylnickel (η(3)-C(3)H(5))(2)Ni.

The manganese carbonyl nitrosyls Mn(NO)(CO)4, Mn2(NO)2(CO)n (n = 7, 6, 5, 4), and Mn3(NO)3(CO)9 have been studied by density functional theory (DFT) using the B3LYP and BP86 methods for comparison of their predicted structures with those of isoelectronic iron carbonyl derivatives. DFT predicts a trigonal bipyramidal structure for Mn(NO)(CO)4 with an equatorial NO group very close to the experimental structure. The predicted lowest energy structure for Mn2(NO)2(CO)7 has two bridging NO groups in contrast to the known structure of the isoelectronic Fe2(CO)9, which has three bridging CO groups. The structures for the unsaturated binuclear Mn2(NO)2(CO)n (n = 6, 5, 4) derivatives are similar to those of the corresponding binuclear iron carbonyls Fe2(CO)n+2 derivatives but always with a preference of bridging NO groups over bridging CO groups. The trinuclear Mn3(NO)3(CO)9 is predicted to have a structure analogous to the known structure for Fe3(CO)12 but with two bridging NO groups rather than two bridging CO groups across one of the metal-metal edges of the M3 triangle. The dark red solid photolysis product of Mn(NO)(CO)4 characterized by its nu(CO) and nu(NO) frequencies approximately 45 years ago is suggested by these DFT studies not to be the originally assumed Mn2(NO)2(CO)7 analogous to Fe2(CO)9. Instead, this photolysis product appears to be Mn2(NO)2(CO)5 with a Mn(triple bond)Mn formal triple bond analogous to (eta5-C5H5)2V2(CO)5 obtained from the photolysis of (eta5-C5H5)V(CO)4.

The trinuclear derivative Fe(3)(C(8)H(8))(3) was synthesized in 2009 by Lavallo and Grubbs via the reaction of Fe(C(8)H(8))(2) with a bulky heterocyclic carbene. This fascinating structure is the first example of a derivative of the well-known Fe(3)(CO)(12) in which all 12 carbonyl groups have been replaced by hydrocarbon ligands. The density functional theory predicts a structure having a central Fe(3) equilateral triangle with ∼2.9 Å Fe-Fe single bonded edges bridged by η(5),η(3)-C(8)H(8) ligands. This structure is close to the experimental structure, determined by X-ray crystallography. The related hypoelectronic M(3)(C(8)H(8))(3) derivatives (M = Cr, V, Ti) are predicted to have central scalene M(3) triangles with edge lengths and Wiberg bond indices (WBIs) corresponding to one formal single M-M bond, one formal double M═M bond, and one formal triple M≡M bond. For Mn(3)(C(8)H(8))(3), both a doublet structure with one Mn═Mn double bond and two Mn-Mn single bonds in the Mn(3) triangle, and a quartet structure with two Mn═Mn double bonds and one Mn-Mn single bond are predicted. The hyperelectronic derivatives M(3)(C(8)H(8))(3) have weaker direct M-M interactions in their M(3) triangles, as indicated by both the M-M distances and the WBIs. Thus, Ni(3)(C(8)H(8))(3) has bis(trihapto) η(3),η(3)-C(8)H(8) ligands bridging the edges of a central approximately equilateral Ni(3) triangle with long Ni···Ni distances of ∼3.7 Å. The WBIs indicate very little direct Ni-Ni bonding in this Ni(3) triangle and thus a local nickel environment in the singlet Ni(3)(C(8)H(8))(3) similar to that observed for diallylnickel (η(3)-C(3)H(5))(2)Ni.

The iron carbonyl nitrosyls Fe 2(NO) 2(CO) n ( n = 7, 6, 5, 4, 3) have been studied by density functional theory (DFT) using the B3LYP and BP86 methods, for comparison of their predicted structures with those of isoelectronic cobalt carbonyl derivatives. The lowest energy structures for Fe 2(NO) 2(CO) 7 and Fe 2(NO) 2(CO) 6 have two NO bridges, and the lowest energy structure for Fe 2(NO) 2(CO) 5 has a single NO bridge with metal-metal distances (BP86) of 3.161, 2.598, and 2.426 A, respectively, corresponding to the formal metal-metal bond orders of zero, one, and two, respectively, required for the favored 18-electron configuration for the iron atoms. The heptacarbonyl Fe 2(NO) 2(CO) 7 is thermodynamically unstable with respect to CO loss to give Fe 2(NO) 2(CO) 6. The favored structures for the more highly unsaturated Fe 2(NO) 2(CO) 4 and Fe 2(NO) 2(CO) 3 also have bridging NO groups but avoid iron-iron bond orders higher than two by formal donation of five electrons from bridging NO groups with relatively short Fe-O distances. The lowest energy structures of the unsaturated Fe 2(NO) 2(CO) n derivatives ( n = 5, 4, 3) are significantly different from the isoelectronic cobalt carbonyls Co 2(CO) n +2 owing to the tendency for Fe 2(NO) 2(CO) n to form structures with bridging NO groups and metal-metal formal bond orders no higher than two.

The binuclear cyclopentadienylmetal nitrosyls and carbonyls Cp 2 M 2 (AO) n (A = N, M = Fe, Co, Ni; A = C, M = Ni; n = 2, 1) are studied by density functional theory using the B3LYP and BP86 functionals. In general, structures with bridging AO ligands are energetically preferred over those with terminal AO ligands. Thus, the global minima for Cp 2 M 2 (AO) 2 are all found to have closely related axial dimetallocene structures with two symmetrically bridging AO ligands but variable planarity of the central M(μ-AO) 2 M units. Similarly, the single AO ligands in the global minima for Cp 2 M 2 (AO) are found to bridge symmetrically the pair of metal atoms. However, structures with terminal AO groups and a single bridging Cp ligand are also found at accessible energies for CpM 2 (NO)(μ-Cp) (M = Fe and Co) and CpNi 2 (CO)(μ-Cp). The metal-metal bond distances in Cp 2 M 2 (AO) n derivatives correlate reasonably well with the requirements of the 18-electron rule. In this connection, the unusual dimer Cp 2 Ni 2 (μ-NO) 2 has a Ni-Ni bond distance suggestive of a single bond and geometry suggesting one one-electron donor bridging NO group and one three-electron donor bridging NO group. However, dissociation of Cp 2 Ni 2 (μ-NO) 2 into the well-known stable monomer CpNiNO is highly favored energetically.

The binuclear cyclopentadienyliron carbonyls Cp2Fe2(CO)n (n = 4, 3, 2, 1; Cp = eta(5)-C5H5) have been studied by density functional theory (DFT) using the B3LYP and BP86 methods. The trans- and cis-Cp2Fe2(CO)2(mu-CO)2 isomers of Cp2Fe2(CO)4 known experimentally are predicted by DFT methods to be genuine minima with no significant imaginary vibrational frequencies. The energies of these two Cp2Fe2(CO)2(mu-CO)2 structures are very similar, consistent with the experimental observation of an equilibrium between these isomers in solution. An intermediate between the interconversion of the trans- and cis-Cp2Fe2(CO)2(mu-CO)2 dibridged isomers of Cp2Fe2(CO)4 can be the trans unbridged isomer of Cp2Fe2(CO)4 calculated to be 2.3 kcal/mol (B3LYP) or 9.1 kcal/mol (BP86) above the global minimum trans-Cp2Fe2(CO)2(mu-CO)2. For the unsaturated Cp2Fe2(CO)3, the known triplet isomer Cp2Fe2(mu-CO)3 with an Fe=Fe double bond similar to the O=O double bond in O2 is found to be the global minimum. The lowest-energy structure for the even more unsaturated Cp2Fe2(CO)2 is a dibridged structure Cp2Fe2(mu-CO)2, with a short Fe-Fe distance suggestive of the Fe[triple bond]Fe triple bond required to give both Fe atoms the favored 18-electron configuration. Singlet and triplet unbridged structures for Cp2Fe2(CO)2 were also found but at energies considerably higher (20-50 kcal/mol) than that of the global minimum Cp2Fe2(mu-CO)2. The lowest-energy structure for Cp2Fe2(CO) is the triplet unsymmetrically bridged structure Cp2Fe2(mu-CO), with a short Fe-Fe distance (approximately 2.1 A) suggestive of the sigma + 2pi + (2/2)delta Fe[quadruple bond]Fe quadruple bond required to give both Fe atoms the favored 18-electron rare gas configuration.