Journal of Organometallic Chemistry 694 (2009) 1781–1785
Journal of Organometallic Chemistry
Communication
Synthesis and X-ray investigation of novel Fe and Mn phenyltellurenyl-halide
complexes: (CO)3FeBr2(PhTeBr), (
g
5-C5H5)Fe(CO)2(PhTeI2) and CpMn(CO)2(PhTeI)
a
b
Yury Torubaev a, , Alexander Pasynskii , Pradeep Mathur
*
a N.S. Kurnakov Institute of General and Inorganic Chemistry, Russ. Acad. Sci. 119991 Moscow, GSP-1, Leninsky Prospect, 31, Russian Federation
b Chemistry Department, Indian Institute of Technology, Powai, Bombay 400076, India
a r t i c l e i n f o
a b s t r a c t
Article history:
New complexes of transition metals with organotellurium halide ligands are reported. Iodination of
Received 22 October 2008
Received in revised form 27 January 2009
Accepted 30 January 2009
Available online 5 February 2009
[CpMn(CO)2]2(l-Ph2Te2) leads to the Te–Te bond cleavage and formation of CpMn(CO)2(PhTeI). Oxidative
addition of PhTeBr3 to Fe(CO)5 gives the monomeric complex (CO)3FeBr2(PhTeBr) which is isostructural
with the recently reported (CO)3FeI2(PhTeI). Insertion of phenyltellurenyl iodide (PhTeI) into the Fe–I
bond of CpFe(CO)2I forms CpFe(CO)2(TeI2Ph). Molecular structures of the reported complexes were deter-
mined by single-crystal X-ray diffraction analysis (XRD). A considerable shortening of metal–tellurium
distances is observed.
Keywords:
Metal carbonyls
Cyclopentadienyl complexes
Tellurenyl
Ó 2009 Elsevier B.V. All rights reserved.
Organotellur compounds
Iron
Manganese
1. Introduction
radii [4] and a secondary bonding between the tellurium atom and
one of the iodide ligands (Te–I (1) 3.1634(5) Å, I–Teꢀ ꢀ ꢀI
The strong multiple bonds between transition metal (M) and
non-transition group 16 elements (E) attract considerable attention
[1]. Normally, such bonds are formed due to the additional p-inter-
162.197(15)°). Fe–Te distance in 1 is quite close to 2.585(2) Å in
(CO)3FeI2(Ph2Te) [2], so additional Te–I(1) interaction in 1 does not
affect metal–tellurium bonding and the observed shortening of
action between the E lone electron pairs and the vacant d-orbitals of
Fe–Te bonds in both cases is a result of Te–Fe r-bonding and dative
M in formally unsaturated complexes (MeC5H4)Cr(CO)2S(C5H4FeC5
Fe–Te interaction with the participation of vacant d-orbitals of Te.
The other pattern for the interaction between PhTeX (X = Br, I)
and organometallic species is the insertion of PhTeX fragment into
the metal–halogen bond. In4 we demonstrated that treatment of
H5) (Cr-S 2.136(1) Å)1 and [(MeC5H4)Cr(CO)2]2(
l-S) (Cr–S 2.073 Å,
Cr–S–Cr 175.6°)2. The ordinary Cr–S bond distance in the dimeric
saturated complex [Cp0Cr(CO)2S(C5H4Mn(CO)3]2 is 2.452(1) Å1. In
this work we have investigated the possibility of M–Te partial mul-
tiple bonding in formally saturated complexes by means of Te
LUMO back-bonding with d-electrons of M.
Recently we reported the oxidative addition of PhTeI3 to Fe(CO)5
to yield an unusual complex (CO)3FeI2(PhTeI)3 (1) which was the
first example of a transition metal complex with unstable aryltel-
lurenyl halide ligand PhTeI. Stabilization of PhTeI in 1 was achieved
due to the formation of a Fe–Te bond (Te–Fe (2.5451(6) Å) which is
reduced on 0.15 Å in comparison with the sum of Fe and Te covalent
(g g
4-C4Me4)Co(CO)2I with PhTeI gives ( 4-C4Me4)Co(CO)2(TeI2Ph)
(2) with a Co–Te bond (2.5470(7) Å) reduced on 0.09 Å as compared
to the sum of Co and Te covalent radii [4] and TeI2Ph ligand with a
Te–I bonds (2.9503(6) and 2.9862(6) Å which are lengthened on
average on 0.2 Å in comparison with the sum of corresponding cova-
lent radii [4]). In 2 the shortening of Co–Te bond could be the result
of Te–Co
r-bonding and dative interaction between Co atom and
Te–I antibonding orbital (Scheme 1).
As part of our ongoing interest in unusual reactivity and molec-
ular structure of metal–aryltellur–halogenide complexes and our
interest in complexes with PhTeI coordinated exclusively with a
metal center without any additional secondary intramolecular
bonds, we have looked into the chemistry of CpMn(CO)2(PhTeI)
(3). Absence of M–I bonds in 3 would suggest that additional
* Corresponding author. Tel.: +7 495 9543841.
1
A. Pasynskii, I.V. Skabitsky, Yu.V. Torubaev, Zh.V. Dobrokhotova, E.V. Krasil’nikova,
Russ. J. Inorg. Chem. 50 (2005) 1197.
2
A.A. Pasynskii, F.S. Denisov, A.N. Grechkin, I.V. Skabitsky, Yu.V. Torubaev, J.V.
4
Dobrokhotova, G.G. Alexandrov, R.A. Lyssenko. Russ. J. Inorg. Chem. 46 (2001) 1990.
Yu.V. Torubaev, A.A. Pasynskii, A.R. Galustian, P. Mathur, Russ. J. Coord. Chem., 35
3
Yu.V. Torubaev, A.A. Pasynskii, P. Mathur, Russ. J. Coord. Chem. 11 (2008) 799.
(2009) 1.
0022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.01.052