M. Sanchez et al., 1-SIGMA(4),2-SIGMA(X)-DIPHOSPHETES (X=2-6) - ON THE PERSISTENCE OF THE P-P BOND, Journal of the American Chemical Society, 119(41), 1997, pp. 9720-9728
Irradiation of [bis(diisopropylamino)phosphino] (trimethylsilyl)diazom
ethane at 254 nm in the presence of tert-butylphosphaalkyne leads to 1
sigma(4),2 sigma(2)-diphosphete 1 in 90% yield. Derivative 1 reacts w
ith Fe-2(CO)(9) and W(CO)(5)(THF) giving rise to the corresponding eta
(1)-complexes 2 (48% yield) and 3 (75% yield), respectively. When 1 eq
uiv of methyl trifluoromethanesulfonate and elemental selenium is adde
d to derivative 1, the cationic and neutral 1 sigma(4),2 sigma(3)-diph
osphetes 4 and 5 are isolated in 95 and 66% yields, respectively. Addi
tion of 2 equiv of elemental selenium and bis(trimethylsilyl)peroxide
to diphosphete 1 gave rise to 1 sigma(4),2 sigma(4)-diphosphetes 6 (43
% yield) and 7 (84% yield), respectively. eta(1)-(1 sigma(4),2 sigma(2
)-Diphosphete)tungsten complex 3 reacted with bis(trimethylsilyl)perox
ide affording heterocyclic complex 8 (68% yield). Addition of 1 equiv
of tetrachloro-o-benzoquinone (TCBQ) to the cationic 1 sigma(4),2 sigm
a(3)-diphosphete 4 and of 2 equiv to the 1 sigma(4),2 sigma(2)-diphosp
hete 1 affords the 1 sigma(4),2 sigma(5)- and 1 sigma(4),2 sigma(6)-di
phosphetes 9 (86% yield) and 10 (92% yield), respectively. Addition of
TCBQ to the eta(1)-(1 sigma(4),2 sigma(2)-diphosphete)tungsten comple
x 3 affords the eta(1)-(1 sigma(4),2 sigma(4)-diphosphete)complex 11 (
88% yield), which reacts with 2 equiv of trimethylphosphine leading to
the zwitterionic 1 sigma(4),2 sigma(3)-diphosphete 12 (46% yield). Cl
eavage of the Si-C bond of complex 3 with 1 equiv of tetrabutylammoniu
m fluoride hydrate gives eta(1)-(1 sigma(4),2 sigma(2)-diphosphete)com
plex 13 (61% yield), which reacts with TCBQ leading to the cis-1,2-dip
hosphino alkene complex 14 (77% yield). These results demonstrate that
the unsaturated four-membered ring skeleton is a remarkable template
for inducing unusual P-P interactions. However, the presence of two ve
ry bulky substituents on the ethylenic moiety is necessary for the per
sistence of the cyclic structure, when the two phosphorus atoms featur
e a high coordination state. Single crystal X-ray diffraction studies
of derivatives 7 and 11-14 have been carried out.