Treat
ment of 1-P
iPr
2-2-NMe
2-indene (
1a[H]) with either
cis/
trans-(SMe
2)
2PtCl
2 or PtCl
2provided (
![](/i<font color=)
mages/gifchars/kappa.gif" BORDER=0 >
2-
P,N-2-NMe
2-3-P
iPr
2-indene)PtCl
2 (
2) in 84% and 55% yield, respectively, whilethe reaction of
1a[H] with (
![](/i<font color=)
mages/gifchars/eta.gif" BORDER=0 >
4-COD)PtClMe afforded (
![](/i<font color=)
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2-
P,N-2-NMe
2-3-P
iPr
2-indene)PtClMe(
3) in 91% yield. Whereas in the for
mation of
2 and
3 the ligand precursor
1a[H] undergoesa rearrange
ment to give a coordinated 2-NMe
2-3-P
iPr
2-indene (
1b[H]) ligand,
1a[H] reactedcleanly with 0.5 equiv of [(
![](/i<font color=)
mages/entities/
mgr.gif">-SMe
2)PtMe
2]
2 to give (
![](/i<font color=)
mages/gifchars/kappa.gif" BORDER=0 >
2-
P,
N-
1a[H])PtMe
2 (
4a) in 97% yield.The iso
merization of
4a to (
![](/i<font color=)
mages/gifchars/kappa.gif" BORDER=0 >
2-
P,
N-
1b[H])PtMe
2 (
4b) in a THF/
iPrOH
mixture is rapid andallowed for the isolation of
4b in 99% yield. Heating of
4a in CH
2Cl
2 resulted in thequantitative for
mation of
3, while the ther
molysis of
4a in toluene in the presence of SMe
2afforded
5, the apparent product of intra
molecular C-H activation of an NMe group. Thereactivity of
4a with a variety of other two-electron donors, as well as E-H-containingsubstrates (E =
main group frag
ment), is reported. Although NMR spectroscopic evidenceindicated the for
mation of an inter
mediate of the type (
![](/i<font color=)
mages/gifchars/kappa.gif" BORDER=0 >
2-
P,
N-
1[H])Pt(SnPh
3)(Me), as wellas Ph
6Sn
2, in the reaction of
4a with 10 equiv of Ph
3SnH, negligible conversion of Ph
3SnHto Ph
6Sn
2 was obtained when e
mploying 1
mol %
4a as a catalyst. Single-crystal X-raydiffraction data for
2 and
5 are reported.