Synthesis of novel platinum dichalcogenido-complexes by taking advantage of bulky phosphine ligands

Article abstract of DOI:10.1080/10426500212306

The first stable disulfido and diselenido complexes of platinum-bearing bulky phosphine ligands were synthesized by the reaction of the corresponding zerovalent platinum complexes with elemental sulfur and selenium, respectively. The molecular structures

Full text of DOI:10.1080/10426500212306

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Phosphorus, Sulfur, and Silicon and the Related
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Synthesis of Novel Platinum Dichalcogenido-Complexes
by Taking Advantage of Bulky Phosphine Ligands
Kazuto Nagata a , Nobuhiro Takeda a & Norihiro Tokitoh a
a Institute for Chemical Research , Kyoto University , Gokasho, Uji, Kyoto, 611-0011, Japan
Published online: 27 Oct 2010.
To cite this article: Kazuto Nagata , Nobuhiro Takeda & Norihiro Tokitoh (2002) Synthesis of Novel Platinum Dichalcogenido-
Complexes by Taking Advantage of Bulky Phosphine Ligands, Phosphorus, Sulfur, and Silicon and the Related Elements,
177:6-7, 1859-1862, DOI: 10.1080/10426500212306
To link to this article: http://dx.doi.org/10.1080/10426500212306
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Phosphorus, Sulfur and Silicon, 2002, Vol. 177:1859–1862
C
Copyright 2002 Taylor & Francis
1042-6507/02 $12.00 + .00
DOI: 10.1080/10426500290093289
SYNTHESIS OF NOVEL PLATINUM
DICHALCOGENIDO-COMPLEXES BY TAKING
ADVANTAGE OF BULKY PHOSPHINE LIGANDS
Kazuto Nagata, Nobuhiro Takeda, and Norihiro Tokitoh
Institute for Chemical Research, Kyoto University, Gokasho, Uji,
Kyoto 611-0011, Japan
(Received July 29, 2001; accepted December 25, 2001)
The first stable disulfido and diselenido complexes of platinum-bearing
bulky phosphine ligands were synthesized by the reaction of the cor-
responding zerovalent platinum complexes with elemental sulfur and
selenium, respectively. The molecular structures of these complexes were
determined by spectral data, elemental analysis, and X-Ray crystallo-
graphic analysis.
Keywords: Bulky phosphine ligand; platinum disulfido complex;
platinum diselenido complex; three-membered ring
INTRODUCTION
Recently, there has been an increasing interest in the structure
and reactivity of transition metal–chalcogen complexes.1 However,
the chemistry of mononuclear platinum chalcogenido-complexes re-
mained unexplored. We have already reported the synthesis of
tetrachalcogenametallolanes containing a heavier group 14 element
by taking advantage of an efficient steric protection group,
2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (Tbt) group.2 These results
prompted us to examine the synthesis of platinum chalcogenido com-
plexes having bulky ligands. Here, we report the synthesis of the
first platinum dichalcogenido-complexes 1a,b having a PtX2 (X = S,Se)
ring by taking advantage of phosphine ligands bearing an extremely
bulky aryl substituent, i.e., Tbt or 2,6-bis[bis(trimethylsilyl)methyl]-4-
[tris(trimethylsilyl)methyl]phenyl (Bbt) group.
Address correspondence to N. Tokitoh, Institute for Chemical Research, Kyoto
University, Gokasho, Uji, Kyoto 611-0011, Japan. E-mail: tokitoh@boc.kuier-kyoto-u.ac.jp
1859

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K. Nagata et al.
SCHEME 1
RESULTS AND DISCUSSION
Bulky phosphine ligands 1a,b were prepared by the treatment of TbtLi
or BbtLi with PCl3, followed by the addition of MeLi (2 eq). The reac-
tion of 2 molar amounts of phosphines 1a,b with K2PtCl4 gave the cor-
responding platinum dichloride complexes 2a,b. Complexes 2a,b were
reduced by an excess of lithium naphthalenide in THF to give the cor-
responding zerovalent platinum complexes 3a,b, and the successive
addition of elemental sulfur or selenium resulted in the formation of
the corresponding platinum dichalcogenido-complexes 4a,b and 5a,b
in moderate yields. To our knowledge, no disulfido and diselenido com-
plexes of platinum has been reported so far, though platinum dioxygen
complexes have been extensively studied.3 These complexes are the first
examples of complexes having a three-membered PtE2 (E = S, Se) ring
system.
SCHEME 2
These new platinum complexes 4a,b and 5a,b were characterized
by NMR spectrometry, high resolution mass spectrometry, and elemen-
tal analysis, and the molecular structures of 4b and 5b were finally
determined by X-ray crystallographic analysis (for compound 4b, see
Figure 1). In both cases of 4b and 5b, the platinum atom had square

Novel Platinum Dichalcogenido-Complexes
1861
FIGURE 1 ORTEP drawing of 4b with thermal ellipsoids (50% probability).
planar structure, and the Bbt groups were in trans positions with re-
gard to the PtE2 (E = S, Se) plane. The lengths of Pt E and E E bonds
˚
˚
[Pt S: 2.348(3) and 2.337(3) A, S S: 2.077(3) A for 4b (E = S); Pt Se:
˚
˚
2.4491(10) and 2.4658(9) A, Se Se: 2.3363(11) A for 5b (E = Se)] are
similar to those of platinum tetrachalcogenido complexes (Pt S: 2.364
4
˚
˚
˚
(av) A, S S: 2.042 (av) A for (Ph3P)2PtS4; Pt Se: 2.457 (av) A, Se Se:
5
˚
2.331 (av) A for (dppe)PtSe4 [dppe = bis(diphenylphosphino)ethane]),
supporting the three-membered ring structure of the PtE2 moieties.
Although compounds 4a,b and 5a,b are obtained as air-stable in the
solid state, they decomposed in solution to the corresponding phosphine
chalcogenide and metallic platinum standing at room temperature for
several days.
SCHEME 3
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