Catalytic hydrosilation of
1-(trimethylsilyl)-1-buten-3-yne (1) with three kinds of
hydrosilanes
(HSiMePh2, HSiMe2Ph, and
HSiEt3) in CDCl3 at 30 °C in the presence of
a catalytic amount of RuHCl(CO)(PPh3)3 (2) gave five types of
reaction products:
(1E,3E)-CH(SiR3)CHCHCHSiMe3
(3), R3SiCH2CHCHCH2SiMe3 (4),
R3SiCHCCHCH2SiMe3
(5),
(1Z,3E)-CH(SiR3)CHCHCHSiMe3
(6), and
R3SiC⋮CCHCHSiMe3 (7).
Detailed investigations on the stoichiometric reactions of
intermediate ruthenium
species provided definitive evidence for the catalytic mechanism
comprised of two catalytic cycles, the Chalk−Harrod cycle A and the modified Chalk−Harrod cycle
C, and their interconnecting processes B and
D. Product
3 is formed by the insertion of 1 into the Ru−H
bond of 2 followed by the reaction of the resulting
terminal
dienyl complex
Ru(CHCHCHCHSiMe3)Cl(CO)(PPh3)2
(8) with hydrosilane. The latter process
regenerates
2 and the sequence of reactions proceeds catalytically
(cycle A). The reaction of 8 with
hydrosilane is
accompanied by a side reaction giving
Ru(SiR3)Cl(CO)(PPh3)2
(9) and CH2CHCHCHSiMe3
(10), and the
latter is further converted to 4 by hydrosilation (process
B). Silyl complex 9 thus generated in the
system is
the key intermediate for catalytic cycle C. Thus the
insertion of 1 into the Ru−SiR3 bond of
9 via a formal
trans-addition process forms an internal dienylruthenium
complex
Ru[C(CHSiR3)CHCHSiMe3]Cl(CO)(PPh3)2 (11), which reacts with
hydrosilane to give 5 and 6 and to regenerate
9. A part of 11 also undergoes
β-hydrogen elimination to give a dehydrogenative silation product
8 and hydride complex 2. Complex
2 thus
formed resumes catalytic cycle A (process D).
The catalytic intermediates 8, 9, and
11 were identified by
NMR spectroscopy and/or elemental analysis. Factors controlling
the catalytic cycles are discussed on the
basis of the experimental observations.
Binuclear ligands possessing two discrete multidentate N-heterocyclic podand coordination sites connected by a flexible propylene spacer and a rigid m-xylene spacer were synthesized. Treatment of the binuclear ligands with Ni(Oac)2 afforded the bimetallic nickel(II) complexes with two discrete nickel centers. The single-crystal X-ray structure determination of the bimetallic nickel(II) complex with a propylene spacer revealed a little distorted square planar geometry at each nickel center.
A quantitative structure-activity relationship formulated for 59 4-anilinopyrimidines inhibiting reserpine-induced ptosis was applied to the design of new , more active, antidepressant compounds. The utility of correlation equations in designing new congeners is discussed and the designed compounds synthesized show the most active group of the anilinopyrimidines .
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