ISSN:
0044-2313
Keywords:
Rhenium complexes
;
nitrido complexes
;
thionitrosyl complexes
;
nitrido bridges
;
crystal structure
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Mixed-ligand Complexes of Rhenium. IX. Reactions on the Nitrido Ligand of [ReN(Me2PhP)(Et2dtc)2]. Synthesis, Characterization, and Structures of [Re(NBCl3)(Me2PhP)(Et2dtc)2], [Re(NGaCl3)(Me2PhP)(Et2dtc)2], and [Re(NS)Cl(Me2PhP)2(Et2dtc)]BCl3, GaCl3 and S2Cl2 react with the well-known [ReN(Me2PhP)(Et2dtc)2] by attack of the nucleophilic nitrido ligand. Final products of these reactions are [Re(NBCl3)-(Me2PhP)(Et2dtc)2], [Re(NGaCl3)(Me2PhP)(Et2dtc)2], and [Re(NS)Cl(Me2PhP)2Et2dtc)] which have been studied by mass spectrometry, IR spectroscopy and X-ray diffraction.[Re(NBCl3)(Me2PhP)(Et2dtc)2] crystallizes in the triclinic space group P1, Z = 2, a = 8.151(6), b = 9.935(8), c = 18.67(1) Å; α = 94.42(4), β = 97.09(1), γ = 101.35(4)°. The coordination geometry is a distorted octahedron. The equatorial coordination sphere is occupied by one phosphorus and three sulphur atoms. The fourth sulphur atom is in trans position to the Re≡N—B moiety. The almost linear Re≡N—B unit has an Re≡N—B angle of 170.5(3)° with a Re—N bond length of 1.704(3) Å.The analogous [Re(NGaCl3)(Me2PhP)(Et2dtc)2] crystallizes in P21/c with a = 8.138(3), b = 18.279(2), c = 19.880(6) Å; β = 99.81(2)°; Z = 4. Rhenium has a distorted octahedral environment. The Re—N—Ga bond is slightly bent with an angle of 154.5(4)° and a Re—N bond length of 1.695(6) Å.[Re(NS)Cl(Me2PhP)2(Et2dtc)] crystallizes in the triclinic space group P1, Z = 4, a = 9.514(2); b = 16.266(5); c = 18.388(3) Å; α = 88.75(2), β = 76.59(2), γ = 85.50(2)° with two crystallographically independent molecules in the asymmetric unit. Rhenium has a distorted octahedral environment with the chloro ligand in trans position to the almost linear thionitrosyl group. The Re=N bond lengths are 1.795(6) and 1.72(1) Å, respectively, and the N=S distances are 1.55(1) and 1.59(1) Å, respectively.
Notes:
BCl3, GaCl3 und S2Cl2 reagieren mit dem nukleophilen Nitridoliganden von [ReN(Me2PhP)(Et2dtc)2]. Als Endprodukte dieser Reaktionen konnten [Re(NBCl3)(Me2PhP)-(Et2dtc)2], [Re(NGaCl3)(Me2PhP)(Et2dtc)2] und [Re(NS)Cl-(Me2PhP)2(Et2dtc)] isoliert und spektroskopisch sowie strukturell charakterisiert werden.[Re(NBCl3)(Me2PhP)(Et2dtc)2] kristallisiert in der triklinen Raumgruppe P1, Z = 2, a = 8,151(6), b = 9,935(8); c = 18,67(1) Å; α = 94,42(4), β = 97,09(1); γ = 101,35(4)Å. Das Koordinationspolyeder um Rhenium ist ein verzerrtes Oktaeder. Die äquatoriale Koordinationssphäre wird von einem Phosphor- und drei Schwefelatomen besetzt. Das vierte Schwefelatom ist in trans-Stellung zur N—B-Einheit koordiniert. Re≡N—B ist mit einem Winkel von 170,5(3)Å und einem Re—N-Abstand von 1,704(3) Å gebunden.Die Bindungsverhältnisse in [Re(NGaCl3)(Me2PhP)(Et2dtc)2] sind analog. Raumgruppe P21/c mit a = 8,138(3), b = 18,279(2), c = 19,880(6) Å; β = 99,81(2)°; Z = 4. Rhenium ist wiederum verzerrt oktaedrisch koordiniert. Der Re—N—Ga-Winkel ist mit 154,5(4)° deutlich kleiner als im Bortrichlorid-Addukt. Der Bindungsabstand Re—N beträgt 1,695(6) Å.[Re(NS)Cl(Me2PhP)2(Et2dtc)] kristallisiert in der triklinen Raumgruppe P1, a = 9,514(2); b = 16,266(5); c = 18,388(3) Å; α = 88,75(2), β = 76,59(2), γ = 85,50(2)° mit zwei kristallographisch unabhängigen Molekülen in der asymmetrischen Einheit. Re ist nahezu ideal oktaedrisch koordiniert. Der Chloroligand befindet sich in trans-Position zur fast linearen Re=N=S-Gruppierung. Die Bindungsabstände Re=N betragen 1,795(9) bzw. 1,72(1) Å, die Abstände N=S 1,55(1) bzw. 1,59(1) Å.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19966220608
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