1996 Organometallics 2010, 29, 1996–1996
Simple Synthesis of (Triphenylphosphoniomethylidene)(penta-
methylcyclopentadienyl) titanium(IV) Dichloride and Its Re-
action with Carbon Monoxide [Organometallics 2009, 28 ,
5285. DOI: 10.1021/om9005406]. Nazhen Liu, Aichen Wang,
Hongjian Sun, and Xiaoyan Li*
Page 5285. The original title of this note should be replaced
by “Simple Synthesis of (Triphenylphosphoniomethylidene)-
(pentamethyl cyclopentadienyl)titanium(IV) Dichloride and
Its Reaction with Carbon Monoxide”.
Pages 5286-5287. The section “Reduction of [Cp*Ti-
Cl2(-CHdPPh3)] (2) with CO” should be completely repla-
ced by the following text.
Reaction of [Cp*TiCl2(-CH=PPh3)] (2) with CO.
˚
Figure 2. Molecular structure of 4. Selected bond distances (A)
and angles (deg): O1-C12 = 1.284(16), Ti2-O1 = 1.995(10),
Ti2-C12=2.029(16), Ti2-Cl1=2.356(5), Ti2-Cl2=2.290(5),
P4-C13 = 1.762(16), C13-C12 = 1.353(19); O1-Ti2-C12 =
37.2(5), O1-Ti2-Cl2 = 116.5(3), C12-Ti2-Cl2 = 94.5(4), O1-
Ti2-Cl1=88.5(3), C12-Ti2-Cl1=122.1(5), Cl2-Ti2-Cl1=
96.61(19), C12-O1-Ti2=72.8(9), O1-C12-C13=127.1(15),
C13-C12-Ti2 =162.5(13), O1-C12-Ti2 =70.0(8).
The reaction of [Cp*TiCl2(-CHdPPh3)] (2) with carbon
monoxide in diethyl ether affords the insertion product, the
β-phosphonioacyl complex [Cp*TiCl2(OCCH)PPh3] (4), as
red crystals. The IR band at 1488 cm-1 indicates η2 coordi-
nation of the inserted carbonyl group to the titanium center.1
The 1H NMR data shows E/Z isomers in CDCl3 in a ratio of
67:33 with respect to the CdC double bond.
[Cp*TiCl2(OCCH)PPh3] (4). Complex 2 (0.20 g, 3.78 mmol)
was dissolved in diethyl ether (20 mL) and kept under CO
(1 atm) at 0 °C. After it was warmed to room temperature, the
mixture was stirred for another 12 h and then filtered. Complex 4
as red crystals was obtained from a diethyl ether solution. Yield:
0.12 g (56.0%). Anal. Calcd for C30H31Cl2OPTi (4; 557.3 g/mol):
C, 64.66; H, 5.61. Found: C, 64.91; H, 6.02. 1H NMR (300.1
MHz, C6D6, 300 K): δ 2.10 (s, 15H, CH3), 4.47 (d, 2J(HP) =
The molecular structure (Figure 2) of complex 4 reveals that
the titanium center has a tetrahedral coordination geometry
with two chlorine atoms, one Cp* ligand, and one η2-coordi-
nated carbonyl group. With respect to the CdC double bond,
this structure is a Z isomer. The C12-O1 bond length is
2
29.1 Hz, 0.6H, CdCHP), 3.70 (d, J(HP) = 25.5 Hz, 0.4H,
CdCHP), 6.86-7.10, 7.32-7.43 and 7.60-7.68 (m, 15H,
P(C6H5)3). 31P NMR (121.5 MHz, C6D6, 300 K): δ 10.2
(s, 0.6P), 15.5 (s, 0.4P) ppm.
˚
1.284(2) A, between that of a C-O single bond and a CdO
˚
double bond. The C12-C13 bond length (1.353(2) A) is
situated in the region of CdC double-bond distances.
Complex 3 was isolated as a byproduct. This compound is
identical with Floriani’s oxo complex.2 It is thought that the
formation of complex 3 was caused by a small amount of
water in the reaction mixture.
Complex 3 was obtained as brilliant yellow crystals (trace)
and structurally characterized and comfirmed.2
Page 5288. The paragraph “Crystallographic Data for 3.”
should be replaced by the following text.
Crystallographic Data for 4: C30H31Cl2OPTi, Mr=557.29,
In conclusion, an R-phosphoniomethylidene complex of
titanium, [Cp*TiCl2(-CHdPPh3)] (2), was obtained from
transylidation reactions of (pentamethylcyclopentadienyl)-
titanium trichloride, [Cp*TiCl3] ,with 2 equiv of Ph3PdCH2.
The reaction of complex 2 with CO afforded an insertion
product, the β-phosphonioacyl complex [Cp*TiCl2(OCCH)-
PPh3] (4). As a byproduct the trinuclear titanium complex
[Cp*Ti-(μ-O)Cl]3 (3) formed through hydrolysis was identi-
fied by single-crystal X-ray diffraction.2
˚
triclinic, space group P1, a=14.517(11) A, b=15.480(11) A, c=
˚
˚
17.133(13) A, R=88.518(15)°, β=73.931(14)°, γ=63.486(14)°,
3
V=3289(4) A , Z = 4, Dc =1.125 g cm-3, 14 273 collected
˚
reflections, 9600 unique reflections (Rint = 0.0893), θmax
=
23.45°, semiempirical absorption correction R1 = 0.1243 (for
9600 reflections with I>2σ(I)), wR2=0.4114 (all data). The
structure was solved by direct methods and refined with full-
matrix least-squares on all F2 (SHELXL-97) with non-hydro-
gen atoms anisotropic.
Page 5288. Line 9 should read “31P NMR (121.5 MHz,
C6D6, 300 K): δ 16.0 ppm.”
Page 5288. “CCDC-715899 (3)” should be replaced by
“CCDC-763344 (4)”.
Page 5288. The section “[Cp*Ti(μ-Cl)Cl]3 (3).” should be
replaced by the following text.
Supporting Information Available: A CIF file giving crystal-
lographic data for complex 4. This material is available free
(1) Weber, K. Doctoral Thesis, University of W€urzburg, W€urzburg,
Germany, 1994, pp 123-139.
(2) Carofiglio, T.; Floriani, C.; Sgamellotti, A.; Rosi, M.; Rizzoli, C.
J. Chem. Soc., Dalton Trans. 1992, 1081.
DOI: 10.1021/om1001588
Published on Web 03/11/2010
Liu, Nazhen
