Heterobimetallic Complexes with Phenylcyclopentadienyl Ligand: Syntheses and Structures of Tricarbonylchromium−η6,η5-Phenylcyclopentadienyl−Transition Metal Complexes1

A new synthetic method of heterobimetallic complexes bridging with
a π,π-phenylcyclopentadienyl ligand,
tricarbonylchromium−η6,η5-phenylcyclopentadienyl−transition
metal complexes, was developed through the
reactions of
(η6-C6H5C5H5)Cr(CO)3
or its sodium salt with transition metal complexes. The method is
suitable
for most transition metal elements with the advantages of easy
manipulation, mild reaction conditions, and moderate
to high yields. As indicated by 1H NMR spectra, the
interactions between the two π systems of phenyl and
cyclopentadienyl rings were weak. X-ray crystal structures of
seven complexes were studied. Compound 23,
[η6-C6H5Cr(CO)3]2C10H10,
crystallizes in orthorhombic space group Pbca with cell
constants a = 29.616(8) Å,
b = 12.861(5) Å, c = 12.397(7) Å,
V = 4721(6) Å3, Z = 8,
R = 0.045, and Rw = 0.045.
Compound 3, (η6-C6H5C9H7)Cr(CO)3,
crystallizes in monoclinic space group
P21/c with cell constants
a = 7.901(3) Å, b =
14.799(2) Å, c = 12.917(2) Å, β = 99.72(2)°,
V = 1488.7(4) Å3, Z = 4,
R = 0.044, and Rw = 0.051.
Compound 7,
Cr(CO)3(η6,η5-C6H5C5H4)Ti(CO)2(η5-C5H5),
crystallizes in monoclinic space group
P21/c with cell constants
a
= 12.361(4) Å, b = 12.487(6) Å, c
= 12.531(7) Å, β = 93.48(4)°, V = 1930
Å3, Z = 4, R = 0.047, and
Rw =
0.048. Compound 13,
Cr(CO)3(η6,η5-C6H5C5H4)Mo(CO)3Br,
crystallizes in monoclinic space group
P21/c with
cell constants a = 14.685(2) Å, b =
8.509(3) Å, c = 14.960(3) Å, β =
104.46(1)°, V = 1810.0(7) Å3,
Z = 4, R
= 0.037, and Rw = 0.037. Compound
19,
Cr(CO)3(η6,η5-C6H5C9H6)Mn(CO)3,
crystallizes in triclinic space group
P-1 with cell constants
a = 11.660(4) Å, b = 12.578(5) Å,
c = 6.987(2) Å, α = 100.03(3)°, β =
104.19(2)°, γ
= 71.99(3)°, V = 939.3(6) Å3,
Z = 2, R = 0.048, and
Rw = 0.065. Compound 21,
Cr(CO)3(η6,η5-C6H5C5H4)Ru(PPh3)2Cl,
crystallizes with one molecule of EtOH in triclinic space group
P-1 with cell
constants
a = 14.033(4) Å, b = 16.163(6) Å,
c = 10.411(3) Å, α = 104.22(3)°, β =
103.50(2)°, γ = 90.81(3)°, V
=
2219(1) Å3, Z = 2, R =
0.081, and Rw = 0.096. Compound
22,
Cr(CO)3(η6,η5-C6H5C5H4)Co(CO)2,
crystallizes
in orthorhombic space group
P212121 with cell
constants a = 15.083(5) Å, b =
16.391(5) Å, c = 6.351(4) Å,
V
= 1570(1) Å3, Z = 4, R =
0.036, and Rw = 0.039. The
trans configurations of the two metal atoms in
these
molecules were found as expected; the phenyl and cyclopentadienyl or
indenyl rings in the molecules were found
to be not coplanar.

本研究开发了一种新型的合成方法，用于构建通过π,π-苯基环戊二烯基配体连接的杂金属双金属配合物，即三羰基铬-η6,η5-苯基环戊二烯基-过渡金属配合物。该方法通过(η6-C6H5C5H5)Cr(CO)3或其钠盐与过渡金属配合物反应实现。该方法适用于大多数过渡金属元素，具有操作简便、反应条件温和以及产率适中至高的优点。根据1H NMR光谱分析，苯环和环戊二烯基环之间的相互作用较弱。对七个配合物的X射线晶体结构进行了研究。化合物23，[η6-C6H5Cr(CO)3]2C10H10，以Pbca正交晶系结晶，晶胞参数为a = 29.616(8) Å，b = 12.861(5) Å，c = 12.397(7) Å，V = 4721(6) Å3，Z = 8，R = 0.045，Rw = 0.045。化合物3，(η6-C6H5C9H7)Cr(CO)3，以P21/c单斜晶系结晶，晶胞参数为a = 7.901(3) Å，b = 14.799(2) Å，c = 12.917(2) Å，β = 99.72(2)°，V = 1488.7(4) Å3，Z = 4，R = 0.044，Rw = 0.051。化合物7，Cr(CO)3(η6,η5-C6H5C5H4)Ti(CO)2(η5-C5H5)，以P21/c单斜晶系结晶，晶胞参数为a = 12.361(4) Å，b = 12.487(6) Å，c = 12.531(7) Å，β = 93.48(4)°，V = 1930 Å3，Z = 4，R = 0.047，Rw = 0.048。化合物13，Cr(CO)3(η6,η5-C6H5C5H4)Mo(CO)3Br，以P21/c单斜晶系结晶，晶胞参数为a = 14.685(2) Å，b = 8.509(3) Å，c = 14.960(3) Å，β = 104.46(1)°，V = 1810.0(7) Å3，Z = 4，R = 0.037，Rw = 0.037。化合物19，Cr(CO)3(η6,η5-C6H5C9H6)Mn(CO)3，以P-1三斜晶系结晶，晶胞参数为a = 11.660(4) Å，b = 12.578(5) Å，c = 6.987(2) Å，α = 100.03(3)°，β = 104.19(2)°，γ = 71.99(3)°，V = 939.3(6) Å3，Z = 2，R = 0.048，Rw = 0.065。化合物21，Cr(CO)3(η6,η5-C6H5C5H4)Ru(PPh3)2Cl，以P-1三斜晶系结晶，并含有一个乙醇分子，晶胞参数为a = 14.033(4) Å，b = 16.163(6) Å，c = 10.411(3) Å，α = 104.22(3)°，β = 103.50(2)°，γ = 90.81(3)°，V = 2219(1) Å3，Z = 2，R = 0.081，Rw = 0.096。化合物22，Cr(CO)3(η6,η5-C6H5C5H4)Co(CO)2，以P212121正交晶系结晶，晶胞参数为a = 15.083(5) Å，b = 16.391(5) Å，c = 6.351(4) Å，V = 1570(1) Å3，Z = 4，R = 0.036，Rw = 0.039。在这些分子中，两个金属原子的顺式构型如预期所示；分子中的苯环和环戊二烯基或 indenyl 环被发现并非共平面。