TY - JOUR
T1 - New Bridging Mode for Organodiazo Ligands. Molecular Structure of (η5-C5H5)(CO)2W(NNCH3)Cr(CO)5
AU - Hillhouse, Gregory L.
AU - Haymore, Barry L.
AU - Bistram, Sabine A.
AU - Herrmann, Wolfgang A.
PY - 1983/1
Y1 - 1983/1
N2 - The interaction of (η5-C5H5)W(CO)2(N2CH3) with Cr(CO)5(THF) (THF = tetrahydrofuran) gives a binuclear complex containing a bridging organodiazo ligand. Attachment of the Cr(CO)5 group to the organodiazo ligand causes the W-N(1) distance to decrease (0.03 Å) and the N(1)-N(2) distance to increase (0.03 Å). Structural changes in the carbonyl and cyclopentadienyl ligands attached to tungsten are also observed. The geometry about chromium is typical of Cr(CO)5L, where L is an ordinary sp2 hybridized σ-donor ligand. This is the first example of an N,N’ bridging organodiazo ligand, and its relationship to isodiazene (hydrazido(2-)) ligands (W-N-NH-R) is discussed. Important structural parameters include W-N(l) = 1.830 (3) Å, N(1)-N(2) = 1.247 (4) Å, Cr-N(2) = 2.106 (3) Å, W-N(1)-N(2) = 174.4 (3)°, N(1)-N(2)-Cr = 122.3 (3)°, N(1)-N(2)-C(8) = 113.8 (3)°, and C(8)-N(2)-Cr = 123.9(2)°. The X-ray crystal structure of the title complex was determined at -175 °C in space group P21/c with a = 15.257 (6) Å, b = 8.874 (3) Å, c = 13.279 (5) Å, β = 111.39 (1)°, and Z = 4. On the basis of 3168 reflections with Fo2 > 3σ(Fo2), the structure was refined by using full-matrix, least-squares methods to R(F) = 0.021 and Rw(F) = 0.029.
AB - The interaction of (η5-C5H5)W(CO)2(N2CH3) with Cr(CO)5(THF) (THF = tetrahydrofuran) gives a binuclear complex containing a bridging organodiazo ligand. Attachment of the Cr(CO)5 group to the organodiazo ligand causes the W-N(1) distance to decrease (0.03 Å) and the N(1)-N(2) distance to increase (0.03 Å). Structural changes in the carbonyl and cyclopentadienyl ligands attached to tungsten are also observed. The geometry about chromium is typical of Cr(CO)5L, where L is an ordinary sp2 hybridized σ-donor ligand. This is the first example of an N,N’ bridging organodiazo ligand, and its relationship to isodiazene (hydrazido(2-)) ligands (W-N-NH-R) is discussed. Important structural parameters include W-N(l) = 1.830 (3) Å, N(1)-N(2) = 1.247 (4) Å, Cr-N(2) = 2.106 (3) Å, W-N(1)-N(2) = 174.4 (3)°, N(1)-N(2)-Cr = 122.3 (3)°, N(1)-N(2)-C(8) = 113.8 (3)°, and C(8)-N(2)-Cr = 123.9(2)°. The X-ray crystal structure of the title complex was determined at -175 °C in space group P21/c with a = 15.257 (6) Å, b = 8.874 (3) Å, c = 13.279 (5) Å, β = 111.39 (1)°, and Z = 4. On the basis of 3168 reflections with Fo2 > 3σ(Fo2), the structure was refined by using full-matrix, least-squares methods to R(F) = 0.021 and Rw(F) = 0.029.
UR - http://www.scopus.com/inward/record.url?scp=4243855859&partnerID=8YFLogxK
U2 - 10.1021/ic00144a022
DO - 10.1021/ic00144a022
M3 - Article
AN - SCOPUS:4243855859
SN - 0020-1669
VL - 22
SP - 314
EP - 318
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 2
ER -