Organometallics 2003, 22, 1657-1662
1657
P h osp h in id en e- a n d P h osp h id o-Br id ged Com p lexes fr om
a η2-Ar ylth ioxop h osp h a n e Cyclop en ta d ien ylch r om iu m
Com p lex
Zhiqiang Weng, Weng Kee Leong, J agadese J . Vittal, and Lai Yoong Goh*
Department of Chemistry, National University of Singapore, Kent Ridge, Singapore 119260
Received November 12, 2002
The reaction of the η2-arylthioxophosphane complex CpCr(CO)2(SP(H)Ar) (2; Ar ) C6H4-
OCH3) with [CpCr(CO)3]2 (1) at 110 °C led to the isolation of new structurally characterized
complexes: hydridophosphido-bridged Cp2Cr2(CO)4(µ2-H)(µ2-P(H)Ar) (3), bis(phosphido)-
bridged CrdCr doubly bonded Cp2Cr2(CO)2(µ2-P(H)Ar)2 (4), and µ3-phosphinidene cubanes
Cp4Cr4S3(µ3-PAr) (5) and Cp4Cr4S2(µ3-PAr)2 (6), together with CpCr(CO)3H (7) and Cp4Cr4S4
(9) with yields of 4, 11, 16, 32, 5, and 19%, respectively.
Ch a r t 1. Coor d in a tion Mod es of P h osp h in id en e
In tr od u ction
The rich chemistry of metal-carbon, -nitrogen, -oxy-
gen, and -sulfur multiple bonds, particularly with
respect to synthetic applications,1 has spurred interest
in transition-metal phosphinidenes.2 The phosphinidene
ligand is capable of binding to transition metals in a
variety of coordination modessas a two-electron donor
in the bent (η1) form A(i) and the pyramidal (µ2) form
A(ii) and as a four-electron donor in forms A(iii)-A(vi)
(Chart 1).
Terminal phosphinidene metal complexes of the type
A(i) are the analogues of carbene complexes and, like
metal carbenes, have been shown to possess rich reac-
tivity features of both electrophilic and nucleophilic
character.3 While many examples of µ2-bridging phos-
phinidene complexes are known of groups 5 and 6
metals,4a,b,d,h and there are odd examples of Zr,4e,f Co,4c,d
and Pt,4g µ3- and µ4-phosphinidene complexes are lim-
ited in number. The majority of these µ3 complexes
contain the M3(CO)n (n ) 6, 8, 9) cluster moieties of
group 8 metals (M ) Fe,5 M ) Ru, Os6a,b), with some
containing bis µ3 or µ4 ligands, e.g. Fe3(CO)9(µ3-PR)2,5h
Fe4(CO)11(µ3-PR)2,5i (cod)4Rh4(µ4-PPh)2,6d and Ru4(CO)10-
(µ-CO)(µ4-PPh)2.8a Heterometallic examples include
MCo2(µ3-PCy)(CO)9 (M ) Fe, Ru),7a MnFeCo(CO)10(µ-
PR),7b Cp/Cp*WRun(CO)10(µ3-H)(µ3-PPh) (n ) 2, 3),7c and
Ru3(CO)9(µ-Au(PMe2Ph))(µ-H)(µ3-PPh).7d There are some
µ3- and µ4-aminophosphinidene complexes: e.g., (Ph3-
PdNdPPh3)Ru5(CO)13(µ-NO)(µ4-PNiPr2),8b Ru5(CO)10-
(µ-CO)2(µ3-CO)(µ3-PNiPr2)(µ4-NH),8b Ru4(CO)12Pt(CO)-
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* To whom correspondence should be addressed. E-mail: chmgohly@
nus.edu.sg.
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10.1021/om020934r CCC: $25.00 © 2003 American Chemical Society
Publication on Web 03/20/2003