BIOMAT Database Logo BIOMAT Database Logo

Formic Acid Modified Ti(OCHMe(2))(4). Syntheses, Characterization, and X-ray Structures of Ti(4)(&mgr;(4)-O)(&mgr;-O)(OFc)(2)(&mgr;-OR)(4)(OR)(6) and Ti(6)(&mgr;(3)-O)(6)(OFc)(6)(OR)(6) (OFc = O(2)CH; OR = OCHMe(2)). 1998

Timothy J. Boyle, and Todd M. Alam, and Cory J. Tafoya, and Brian L. Scott
Los Alamos National Laboratories, CST-18, Chemical Science and Technology Division, X-ray Diffraction Laboratory, Los Alamos, New Mexico 87545.

Novel structural arrangements for carboxylic acid modified titanium alkoxides were obtained from stoichiometric reactions between titanium isopropoxide (Ti(OPr(i))(4)) and formic acid (HOFc). The 1:1 reaction in toluene forms the tetranuclear species Ti(4)O(2)(OFc)(2)(OPr(i))(10), 1. The structure of 1 was solved in the triclinic space group P&onemacr; with a = 13.034(3) Å, b = 13.467(2) Å, c = 13.996(2) Å, alpha = 98.79(1) degrees, beta = 104.68(2) degrees, and gamma = 97.82(2) degrees for Z = 2. The general structure of 1 resembles two face-shared [Ti-O](4) cubes with one set of mirror-related titanium atoms removed. The oxygen atoms are represented by one &mgr;(4)-O, one &mgr;-O, and four &mgr;-OR ligands, with the remaining sites filled by two OFc ligands and six terminal alkoxides. Increasing the stoichiometry to 1:2 (Ti/HOFc) leads to the isolation of Ti(6)O(6)(OFc)(6)(OR)(6), 2. The structure of 2 was solved in the monoclinic space group P2(1)/c with a = 8.968(2) Å, b = 26.520(4) Å, c = 20.046(2) Å, and beta = 93.19(1) degrees for Z = 4. The structure of 2 consists of two offset six-membered [Ti-(&mgr;(3)-O)](3) rings joined through Ti-O bonds. The OFc ligands are arranged externally around the central hexagon-prism, oscillating between the top and bottom rings. Compound 1 adopts a very symmetrical arrangement in solution due to the labile OFc ligands and was found to undergo "aging" by a trans-esterification mechanism, the rate of which is enhanced by heating. Compound 2 maintains its solid-state structure in solution.

UI MeSH Term Description Entries

Related Publications

Timothy J. Boyle, and Todd M. Alam, and Cory J. Tafoya, and Brian L. Scott
X-ray Structure and Raman Spectrum of [Ti(4)(&mgr;(3)-O)(2)(&mgr;(2)-O(i)()Pr)(2)(O(i)()Pr)(8)(acac)(2)]: Presence of a Ti(4)(&mgr;(3)-O)(2)(&mgr;(2)-O(i)()Pr)(2) Ladder-like Core.
March 1998, Inorganic chemistry,
Timothy J. Boyle, and Todd M. Alam, and Cory J. Tafoya, and Brian L. Scott
Syntheses and Crystal Structures of [K(2.2.2-cryptand)](2)[(&mgr;-O){&mgr;-O(2)Si(CH(3))(2)}(2)(GeSe)(2)] and [K(2.2.2-cryptand)](2)[Sb(2)Se(6)].
August 1997, Inorganic chemistry,
Timothy J. Boyle, and Todd M. Alam, and Cory J. Tafoya, and Brian L. Scott
Heterometallic Osmium-Mercury Chain Structures Linking Two {Os(3)(CO)(10)(&mgr;-X)} Subunits (X = Cl, Br, I): Syntheses and Molecular Structures of [{Os(3)(CO)(10)(&mgr;-X)}(2)(&mgr;(4)-Hg)] (X = Cl, I), [{Os(3)(CO)(10)(&mgr;-Cl)}(2){&mgr;-HgOs(CO)(4)}(2)], and cis-[Os(CO)(4){(&mgr;-Hg)Os(3)(CO)(10)(&mgr;-Cl)}(2)].
May 1997, Inorganic chemistry,
Timothy J. Boyle, and Todd M. Alam, and Cory J. Tafoya, and Brian L. Scott
Synthesis of the Organotitanoxane Complexes [(eta(5)-C(5)Me(5))(4)Ti(4)X(2)](&mgr;-O)(5). X-ray Structure of [(eta(5)-C(5)Me(5))(4)Ti(4)Me(2)](&mgr;-O)(5).
January 1996, Inorganic chemistry,
Timothy J. Boyle, and Todd M. Alam, and Cory J. Tafoya, and Brian L. Scott
Synthesis and Characterization of Neutral Hexanuclear Iron Sulfur Clusters Containing Stair-like [Fe(6)(&mgr;(3)-S)(4)(&mgr;(2)-SR)(4)] and Nest-like [Fe(6)(&mgr;(3)-S)(2)(&mgr;(2)-S)(2)(&mgr;(4)-S)(&mgr;(2)-SR)(4)] Core Structures.
July 1998, Inorganic chemistry,
Timothy J. Boyle, and Todd M. Alam, and Cory J. Tafoya, and Brian L. Scott
[Al(15)(&mgr;(3)-O)(4)(&mgr;(3)-OH)(6)(&mgr;-OH)(14)(hpdta)(4)](3-)-A New Al(15) Aggregate Which Forms a Supramolecular Zeotype H(5)hpdta=HOCH(2)[CH(2)N(CH(2)COOH)(2)](2).
October 2001, Angewandte Chemie (International ed. in English),
Timothy J. Boyle, and Todd M. Alam, and Cory J. Tafoya, and Brian L. Scott
Sulfur-Bridged Cubane-Type Molybdenum-Gallium Clusters with Mo(3)GaS(4)(n)(+) (n = 5, 6) Cores. X-ray Structures of [Mo(3)GaS(4)(H(2)O)(12)](CH(3)C(6)H(4)SO(3))(5).14H(2)O and [Mo(3)GaS(4)(H(2)O)(12)](CH(3)C(6)H(4)SO(3))(6).17H(2)O.
April 1997, Inorganic chemistry,
Timothy J. Boyle, and Todd M. Alam, and Cory J. Tafoya, and Brian L. Scott
Synthesis of Heteronuclear Pt-Tl Complexes with Donor-Acceptor Bonds. X-ray Structures of cis-[Tl(&mgr;(2)-OOCCH(3))Pt(PPh(3))(C(6)F(5))(2)] and (NBu(4))(2)[{Pt(C(6)F(5))(3)}(2){(&mgr;(2)-O,&mgr;(3)-O'CCH(3))Tl}(2)].
March 1997, Inorganic chemistry,
Timothy J. Boyle, and Todd M. Alam, and Cory J. Tafoya, and Brian L. Scott
Experimental and Theoretical Investigation of the Molecular and Electronic Structure of [Zn(4)(&mgr;(4)-S){&mgr;-S(2)As(CH(3))(2)}(6)] and [Cd(4)(&mgr;(4)-S){&mgr;-S(2)As(CH(3))(2)}(6)]: Two Possible Molecular Models of Extended Metal Chalcogenide Semiconductors.
March 1999, Inorganic chemistry,
Timothy J. Boyle, and Todd M. Alam, and Cory J. Tafoya, and Brian L. Scott
Microporous Montmorillonites Expanded with Alumina Clusters and M[(&mgr;-OH)Cu(&mgr;-OCH(2)CH(2)NEt(2))](6)(ClO(4))(3), (M = Al, Ga, and Fe), or Cr[(&mgr;-OCH(3))(&mgr;-OCH(2)CH(2)NEt(2))CuCl](3) Complexes.
May 1999, Inorganic chemistry,
Copied contents to your clipboard!