The Reversible Insertion Reaction of Carbon Dioxide with the W(CO)5OH- Anion. Isolation and Characterization of the Resulting Bicarbonate Complex [PPN][W(CO)5O2COH]
- 1 January 1996
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 35 (15) , 4406-4413
- https://doi.org/10.1021/ic9516525
Abstract
[Et(4)N][W(CO)(5)OH] (1) and [PPN][W(CO)(5)O(2)COH] (2) have been synthesized and characterized by (1)H and (13)C NMR and IR spectroscopies, and the X-ray crystal structure of 2 has been determined. Complex 2 crystallizes in the triclinic space group P&onemacr; with unit cell parameters a = 12.208(2) Å, b = 13.497(2) Å, c = 13.681(2) Å, alpha = 101.06(2) degrees, beta = 114.76(1) degrees, gamma = 98.45(2) degrees, V = 1942.6(5) Å(3), and Z = 2. The structure of the anion of complex 2 consists of a central W(0) bound to five carbonyl ligands, and the coordination around the metal is completed by a monodentate bound bicarbonate ligand located 2.19(1) Å away from the metal center. In the solid state, two anions are hydrogen bonded to one another via the bicarbonate ligands in the unit cell. Complex 1 inserts CO(2), COS, or CS(2) to rapidly afford the corresponding bicarbonate or thiocarbonate complexes. The lower limit for the rate constant for the carboxylation of complex 1 has been determined to be 4.2 x 10(-)(4) M(-)(1) s(-)(1) at -70.2 degrees C, and the lower limit for the rate constant for the decarboxylation of complex 2 has been found to be 2.5 x 10(-)(3) s(-)(1) at 20.0 degrees C. In addition, the rate constant for the decarbonylation of 2 was determined to be 7.60 x 10(-)(3) s(-)(1) at 36.0 degrees C, a value which is somewhat faster than anticipated on the basis of analogous data for a large variety of W(CO)(5)O(2)CR(-) derivatives. This is attributed to a diminution of the electron-withdrawing ability of the OH substituent in O(2)COH as a result of hydrogen bonding to solvent. Nevertheless, it is clear that the rate of decarboxylation of the anion from complex 2 is faster than the rate of CO dissociation. Concomitantly, carboxylation of complex 1 is faster than CO dissociation, since the W(CO)(5)OH(-) is inert toward (13)CO exchange on the time scale of carboxylation at -70.2 degrees C.Keywords
This publication has 71 references indexed in Scilit:
- Structure of native and apo carbonic anhydrase II and structure of some of its anion-ligand complexesJournal of Molecular Biology, 1992
- Tris(3-tert-butylpyrazolyl)hydroborato zinc hydride: synthesis, structure and reactivity of a monomeric zinc hydride derivativeJournal of the Chemical Society, Chemical Communications, 1991
- Insertion of carbon dioxide into metal alkoxide bonds. Synthesis and structure of tungsten tetracarbonyl carbonateJournal of the American Chemical Society, 1987
- Chemical and structural characterization of W(CO)5OPPh2NPPh3. A novel tungsten carbonyl complex containing a phosphine oxide ligand derived from the bis(triphenylphosphine)nitrogen(1+) cationInorganic Chemistry, 1986
- Preparation and structure of W(CO)5OPPh2NPPh3, a novel complex containing a ligand derived from the bis(triphenylphosphine)nitrogen(1+) cationInorganic Chemistry, 1986
- Synthesis and characterization of polynuclear chromium carbonyl tetraanionsInorganic Chemistry, 1985
- An Electronic Mechanism for the Catalysis of Carbonic AnhydraseAnnals of the New York Academy of Sciences, 1984
- Hydration and reduction of carbon dioxide by rhodium hydride compounds. Preparation and reactions of rhodium bicarbonate and formate complexes, and the molecular structure of RhH2(O2COH)(P(i-Pr)3)2Journal of the American Chemical Society, 1979
- Crown ethers in inorganic chemistry. Preparation and characterization of the Group 6 pentacarbonyl hydroxides and fluoridesInorganic Chemistry, 1975
- Polar and Steric Substituent Constants for Aliphatic and o-Benzoate Groups from Rates of Esterification and Hydrolysis of Esters1Journal of the American Chemical Society, 1952