Formation of carbonyl-carbonate complexes of molybdenum by reductive disproportionation of carbon dioxide. X-ray structure of Mo4(.mu.4-CO3)(CO)2(O)2(.mu.2-O)2(.mu.2-OH)4(PMe3)6

Abstract

1493carbon distance is >3.5 A from all of the published X-ray structural data on I-VI. The trial correlations involving the isotropic shieldings (ah), the tensor components and dZ2, and the asymmetry parameters ( q ) , are not good, but excellent correlations are obtained between bj3 and A6 with R (Figures 1 and The reaction of carbon dioxide with the bis(dinitrogen) complex cis-Mo(N2),(PMe,),, in coordinating solvents, gives the carbonyl-arbonate complexes [MO(~~~-~~,~~-CO~)(CO)(PM~~)~], (2) and Mo(CO,)(CO)(PMe,), (3) derived from the metal-induced reductive disproportionation of COP The use of EtzO or THF as the reaction solvent leads to the preferential formation of binuclear 2 whereas in acetone monomeric 3 is the preferred product. Compounds 2 and 3 interconvert readily by association or dissociation of PMe,, and their solution stabilities have been found to be strongly solvent dependent. Interaction of 3 with the chelating phosphines dmpe or dmpm (dmpe = Me2PCH2CH,PMe2; dmpm = Me,PCH2PMe2), under appropriate conditions, affords the related complexes Mo(CO$OO)(P-P!(PM~,)~ (P-P = dmpe, 4; P-P = dmpm, 5) and Mo(CO,)(CO)(dmpe), (6). Compounds 2 and 3 react with H20 with formation of an unusual tetrametallic, mixed-valence Mo(I1)-Mo(V) complex M04(fi4-CO,)-(C0)2(0)2(~2-0)2(~2-OH)4(PMe,)6 (7) that contains a unique carbonate ligand engaged in a novel type of bonding. The structure of 7 has been determined by X-ray crystallography. Crystals of 7 are orthorhombic, Pbcn, with unit cell constants a = 26.866 (9) A, b = 12.934 (4) A, c = 11.965 (2) A, and D(calcd) = 1.74 g for Z = 4. [MO(~~-T$,~~-CO~)(CO)(PM~~)~]~ (2) or the monomeric, dark-Alvarez et al. (a) Inoue, S.; Yamazaki, N. Organic and Bio-organic Chemistry of Carbon Dioxide; Halsted Press: Tokyo, Japan, 1982. (b) Palmer, D. A.; Van Eldik, R. Chem. Rev. 1983,83, 651. Chatt, J.; Kubota, M.; Leigh, G. J.; March, T. C.; Mason, R.; Yarrow, D. J. J. Chem. Soc., Chem. Commun. 1974, 1033. (a) Carmona, E.; Palma, P.; Paneque, M.; Poveda, M. L.; Gutierrez-Puebla. E.; Monge, A. J. Am. Chem. Soc. 1986,108,6424. (b) Carmona, E.; Gutibrrez-Puebla, E.; Marin, J. M.; Monge, A.; Paneque, M.; Poveda, M. L.; Ruiz, C. J . Am. Chem. Soc. 1989, 1 1 1 , 2883. (c) Carmona, E.; M a r k J. M.; Palma, P.; Paneque, M.; Poveda, M. L. Inorg. Chem. 1989, 28, 1895. Reinking. M. K.; Ni, J.; Fanwick, P. E.; Kubiak, C. P. J. Am. Chem. Soc. 1989, 111, 6454. For mononuclear, structurally characterized M X O , complexes see: (a) Alvarez, R.; Carmona, E.; Marin, J. M.; Poveda, M. L.; GutiQrez-Pucbla. E.; Mongc, A. J. Am. Chem. Soc. 1986,108,2286. (b) Aresta, M.; Nobile, C. F.; Albano, V. G.; Forni, E.; Manassero, M. J. Chem. Soc., Chem. Commun. 1975.36. (c) Bristow, G. S.; Hitchcock, P. 9.; Lappert, M. F. For a preliminary communication-of this work, see: Carmona, E.; GonzBlez, F.; Poveda. M. L.; Marin, J. M. J. Am. Chem. SOC. 1983, 105, 3365.

Reactions of Copper and Silver Cations with Carbon Dioxide: An Infrared Photodissociation Spectroscopic and Theoretical Study

“…Similar blue-shifted bands for the CO 2 ligands attached directly to the metal have also been observed for Mg + , Al + , Si + , V + , Fe + , and Ni + . ,,,,,, In contrast, the oxide-carbonyl structure has been found for Ti + . A carbonyl-carbonate structure has been observed for molybdenum in the Mo 4 (μ 4 -CO 3 )­(CO) 2 (O) 2 (μ 2 –O) 2 ­(μ 2 –OH) 4 (PMe 3 ) 6 complex derived from the metal-induced reductive disproportionation of carbon dioxide . Matrix-isolation infrared spectroscopic studies reveal that the early lanthanoid (La–Sm) oxocarbonyl complexes adopt the trans-configurations, the europium and ytterbium ones adopt side-on-bonded modes (Eu-(η 2 -OC)O and Yb-(η 2 -OC)­O), and the late lanthanoid (Gd–Lu) ones adopt the cis-configurations .…”

“…15 A carbonylcarbonate structure has been observed for molybdenum in the Mo 4 (μ 4 -CO 3 )(CO) 2 (O) 2 (μ 2 −O) 2 (μ 2 −OH) 4 (PMe 3 ) 6 complex derived from the metal-induced reductive disproportionation of carbon dioxide. 36 Matrix-isolation infrared spectroscopic studies reveal that the early lanthanoid (La−Sm) oxocarbonyl complexes adopt the trans-configurations, the europium and ytterbium ones adopt side-on-bonded modes (Eu-(η 2 -OC)O and Yb-(η 2 -OC)O), and the late lanthanoid (Gd−Lu) ones adopt the cis-configurations. 37 Interestingly, recent infrared photodissociation spectroscopic study of [V(CO 2 ) n ] + allows identification of an oxalate-type C 2 O 4 anion species at n = 7.…”

Crystal structure of dodecaaqua-tetra-μ3-carbonato-hexa(N,N,N',N'- tetramethylethylenediamine)hexanickel(II) hemiheptabromide hemihydroxide, [{Ni2(C6H16N2)2(H2O)4(CO3)1.33}3][Br]3.5[OH]0.5

“…Another interest is the potential CO 2 fixation by nickel complexes in basic solutions and the subsequent crystallization of the nickel carbonate complexes [9][10][11]. To date, only six modes of coordination by the carbonate anion have been described which involve two to three metal centers, with some of the carbonate oxygen atoms bonding to one or two metals [12][13][14][15][16]. Multinuclear cluster complexes having as much as 6metal centers are small in number [17][18][19][20][21] and the high symmetry cluster described here is, as far as we know, not precedented, where each carbonate oxygen atom bonds to adifferent nickel center.…”

Reaction of a Molybdenum Bis(dinitrogen) Complex with Carbon Dioxide: A Combined Experimental and Computational Investigation

“…A third product was also obtained, which was found to be trans-[(PMe 3 ) 4 Mo-(CO 2 ) 2 ] (Figure 2, D) in subsequent publications. 30,31 The trans-orientation of the CO 2 ligands in this complex appears unproductive for disproportionation; however, the authors proposed that head-to-tail reductive coupling could be responsible, and the key metallacyclic intermediate (Figure 2, E) has been discussed. 29,31 Additional Mo-based CO 2 disproportionation studies have yielded limited mechanistic information.…”