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Title: Reactions of niobocene derivatives with GaCl/sub 3/ and InCl/sub 3/. Synthesis and molecular structure of carbonylchlorobis(cyclopentadienyl)niobium Cp/sub 2/Nb(CO)Cl, the binuclear. mu. -oxo complex ((CH/sub 3/C/sub 5/H/sub 4/)/sub 2/NbCl)/sub 2/O, and the pentanuclear complex containing an Nb-In-Nb-In-Nb metal chain ((CH/sub 3/C/sub 5/H/sub 3/)/sub 2/NbH)/sub 3/ (. mu. -InCl)/sub 2/ (in Russian)

Abstract

The reactions of Cp/sub 2/Nb(CO)H (I) with MCl/sub 3/ (M = Ga and In) in THF in the presence of Et/sub 3/N have been studied for the purpose of obtaining complexes with Nb-Ga and Nb-In bonds. However, only mixtures of unidentified oily substances form under these conditions. The same reaction with M = Ga in the presence of BuLi gives only Cp/sub 2/Nb(CO)Cl (II). The reaction of (CH/sub 3/C/sub 4/H/sub 4/)/sub 2/NbGH/sub 4/-Et/sub 3/N-BuLi systems with MCl/sub 3/ in THF results in the formation of the binuclear complex ((CH/sub 3/C/sub 5/H/sub 4/)/sub 2/NbCl)/sub 2/O (III) in the case of M = Ga and the appearance of the pentanuclear complex ((CH/sub 3/C/sub 5/H/sub 4/)/sub 2/NbH)/sub 3/(..mu..-InCl)/sub 2/ (IV) when M = In. The structures of complexes II-IV have been established by x-ray diffraction analysis. Complex II contains a tapered sandwich fragment with a 44.4/sup 0/ Angle between the rings ((Nb-C)/sub av/ = 2.37 A) and with a Cl atom (Nb-Cl = 2.557 A) and a terminal CO group (Nb-C(CO) = 2.03(1), C-O = 1.15(1) A) in the bisecting plane of the angle between the rings. In complex III the two (CH/sub 3/C/sub 5/H/sub 4/)/sub 2/Nb fragments (Nb-C(MeCp) = 2.40(4) A) aremore » joined by a practically linear Nb single bond O single bond Nb bridge (Nb-O = 1.924(3) A, NbONb = 172.77/sup 0/), and each Nb atom is bonded to one terminal chlorine atom (Nb-Cl = 2.504(7) A), which is located in the transposition relative to the NbONb fragment (ClNbO = 86.06/sup 0/). In complex IV the three (CH/sub 3/C/sub 5/H/sub 4/)/sub 2/Nb fragments are joined by two InCl groupings to form Nb-In bonds (Nb/sub t/-In = 2.77(1), Nb/sub c/-In = 2.87(1) a), which are observed for the first time, in an Nb-In-Nb-In-Nb metal chain, which lies in a single plane (the NbInNb angles equal 145 and 140, and the InNbIn angle equals 65/sup 0/). The In atoms are at a nonbonding distance (3.13 A) and are weakly bonded to the bridging Cl atoms (In-Cl = 2.97(2) A, In-Cl = 2.97(2) A, InClIn = 64.0(4)/sup 0/).« less

Authors:
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Publication Date:
OSTI Identifier:
6509297
Alternate Identifier(s):
OSTI ID: 6509297
Resource Type:
Journal Article
Resource Relation:
Journal Name: Sov. J. Coordinat. Chem.; (United States); Journal Volume: 11:7; Other Information: Translated from Koordinatsionnaya Khimiya; 11: No. 7, 995-1002(Jul 1985)
Country of Publication:
United States
Language:
Russian
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CARBONYLS; MOLECULAR STRUCTURE; SYNTHESIS; GALLIUM CHLORIDES; COMPLEXOMETRY; INDIUM CHLORIDES; NIOBIUM COMPLEXES; BOND ANGLE; BOND LENGTHS; CATALYTIC EFFECTS; CHEMICAL BONDS; COORDINATION VALENCES; CRYSTALLIZATION; CYCLOPENTADIENE; LATTICE PARAMETERS; NIOBIUM CHLORIDES; NIOBIUM HYDRIDES; SPACE GROUPS; X-RAY DIFFRACTION; ALKENES; CHLORIDES; CHLORINE COMPOUNDS; COHERENT SCATTERING; COMPLEXES; CYCLOALKENES; DIENES; DIFFRACTION; DIMENSIONS; GALLIUM COMPOUNDS; HALIDES; HALOGEN COMPOUNDS; HYDRIDES; HYDROCARBONS; HYDROGEN COMPOUNDS; INDIUM COMPOUNDS; LENGTH; NIOBIUM COMPOUNDS; ORGANIC COMPOUNDS; PHASE TRANSFORMATIONS; POLYENES; REFRACTORY METAL COMPOUNDS; SCATTERING; TRANSITION ELEMENT COMPLEXES; TRANSITION ELEMENT COMPOUNDS; VALENCE 400201* -- Chemical & Physicochemical Properties

Citation Formats

Skripkin, Yu.V., Eremenko, I.L., Pasynskii, A.V., Volkov, O.G., Bakum, S.I., Porai-Koshits, M.A., Antsyshkina, A.S., Dikareva, L.M., Ostrikova, V.N., Sakharov, S.G., and Struchkov, Yu.T. Reactions of niobocene derivatives with GaCl/sub 3/ and InCl/sub 3/. Synthesis and molecular structure of carbonylchlorobis(cyclopentadienyl)niobium Cp/sub 2/Nb(CO)Cl, the binuclear. mu. -oxo complex ((CH/sub 3/C/sub 5/H/sub 4/)/sub 2/NbCl)/sub 2/O, and the pentanuclear complex containing an Nb-In-Nb-In-Nb metal chain ((CH/sub 3/C/sub 5/H/sub 3/)/sub 2/NbH)/sub 3/ (. mu. -InCl)/sub 2/. United States: N. p., 1986. Web.
Skripkin, Yu.V., Eremenko, I.L., Pasynskii, A.V., Volkov, O.G., Bakum, S.I., Porai-Koshits, M.A., Antsyshkina, A.S., Dikareva, L.M., Ostrikova, V.N., Sakharov, S.G., & Struchkov, Yu.T. Reactions of niobocene derivatives with GaCl/sub 3/ and InCl/sub 3/. Synthesis and molecular structure of carbonylchlorobis(cyclopentadienyl)niobium Cp/sub 2/Nb(CO)Cl, the binuclear. mu. -oxo complex ((CH/sub 3/C/sub 5/H/sub 4/)/sub 2/NbCl)/sub 2/O, and the pentanuclear complex containing an Nb-In-Nb-In-Nb metal chain ((CH/sub 3/C/sub 5/H/sub 3/)/sub 2/NbH)/sub 3/ (. mu. -InCl)/sub 2/. United States.
Skripkin, Yu.V., Eremenko, I.L., Pasynskii, A.V., Volkov, O.G., Bakum, S.I., Porai-Koshits, M.A., Antsyshkina, A.S., Dikareva, L.M., Ostrikova, V.N., Sakharov, S.G., and Struchkov, Yu.T. Thu . "Reactions of niobocene derivatives with GaCl/sub 3/ and InCl/sub 3/. Synthesis and molecular structure of carbonylchlorobis(cyclopentadienyl)niobium Cp/sub 2/Nb(CO)Cl, the binuclear. mu. -oxo complex ((CH/sub 3/C/sub 5/H/sub 4/)/sub 2/NbCl)/sub 2/O, and the pentanuclear complex containing an Nb-In-Nb-In-Nb metal chain ((CH/sub 3/C/sub 5/H/sub 3/)/sub 2/NbH)/sub 3/ (. mu. -InCl)/sub 2/". United States.
@article{osti_6509297,
title = {Reactions of niobocene derivatives with GaCl/sub 3/ and InCl/sub 3/. Synthesis and molecular structure of carbonylchlorobis(cyclopentadienyl)niobium Cp/sub 2/Nb(CO)Cl, the binuclear. mu. -oxo complex ((CH/sub 3/C/sub 5/H/sub 4/)/sub 2/NbCl)/sub 2/O, and the pentanuclear complex containing an Nb-In-Nb-In-Nb metal chain ((CH/sub 3/C/sub 5/H/sub 3/)/sub 2/NbH)/sub 3/ (. mu. -InCl)/sub 2/},
author = {Skripkin, Yu.V. and Eremenko, I.L. and Pasynskii, A.V. and Volkov, O.G. and Bakum, S.I. and Porai-Koshits, M.A. and Antsyshkina, A.S. and Dikareva, L.M. and Ostrikova, V.N. and Sakharov, S.G. and Struchkov, Yu.T.},
abstractNote = {The reactions of Cp/sub 2/Nb(CO)H (I) with MCl/sub 3/ (M = Ga and In) in THF in the presence of Et/sub 3/N have been studied for the purpose of obtaining complexes with Nb-Ga and Nb-In bonds. However, only mixtures of unidentified oily substances form under these conditions. The same reaction with M = Ga in the presence of BuLi gives only Cp/sub 2/Nb(CO)Cl (II). The reaction of (CH/sub 3/C/sub 4/H/sub 4/)/sub 2/NbGH/sub 4/-Et/sub 3/N-BuLi systems with MCl/sub 3/ in THF results in the formation of the binuclear complex ((CH/sub 3/C/sub 5/H/sub 4/)/sub 2/NbCl)/sub 2/O (III) in the case of M = Ga and the appearance of the pentanuclear complex ((CH/sub 3/C/sub 5/H/sub 4/)/sub 2/NbH)/sub 3/(..mu..-InCl)/sub 2/ (IV) when M = In. The structures of complexes II-IV have been established by x-ray diffraction analysis. Complex II contains a tapered sandwich fragment with a 44.4/sup 0/ Angle between the rings ((Nb-C)/sub av/ = 2.37 A) and with a Cl atom (Nb-Cl = 2.557 A) and a terminal CO group (Nb-C(CO) = 2.03(1), C-O = 1.15(1) A) in the bisecting plane of the angle between the rings. In complex III the two (CH/sub 3/C/sub 5/H/sub 4/)/sub 2/Nb fragments (Nb-C(MeCp) = 2.40(4) A) are joined by a practically linear Nb single bond O single bond Nb bridge (Nb-O = 1.924(3) A, NbONb = 172.77/sup 0/), and each Nb atom is bonded to one terminal chlorine atom (Nb-Cl = 2.504(7) A), which is located in the transposition relative to the NbONb fragment (ClNbO = 86.06/sup 0/). In complex IV the three (CH/sub 3/C/sub 5/H/sub 4/)/sub 2/Nb fragments are joined by two InCl groupings to form Nb-In bonds (Nb/sub t/-In = 2.77(1), Nb/sub c/-In = 2.87(1) a), which are observed for the first time, in an Nb-In-Nb-In-Nb metal chain, which lies in a single plane (the NbInNb angles equal 145 and 140, and the InNbIn angle equals 65/sup 0/). The In atoms are at a nonbonding distance (3.13 A) and are weakly bonded to the bridging Cl atoms (In-Cl = 2.97(2) A, In-Cl = 2.97(2) A, InClIn = 64.0(4)/sup 0/).},
doi = {},
journal = {Sov. J. Coordinat. Chem.; (United States)},
number = ,
volume = 11:7,
place = {United States},
year = {Thu May 01 00:00:00 EDT 1986},
month = {Thu May 01 00:00:00 EDT 1986}
}