New Acetonyl Palladium(II) Complexes - Universidad de Murcia

New Acetonyl Palladium(II) Complexes Organometallics, Vol. 27, No. 15, 2008 3983
Figure 2. Ellipsoid representation of complex 8 (50% probability).
Selected bond lengths (Å) and angles (deg): Pd-N(31) ) 2.0269(18),
Pd-N(21) ) 2.0328(18), Pd-C(1) ) 2.056(2), Pd-N(11) )
2.1202(19), C(1)-C(2) ) 1.464(4), O(1)-C(2) ) 1.229(3),
C(2)-C(3))1.512(3),N(31)-Pd-C(1))89.60(9),N(21)-Pd-C(1)
) 90.56(9), N(31)-Pd-N(11) ) 89.83(7), N(21)-Pd-N(11) )
89.96(7), C(2)-C(1)-Pd ) 108.20(16), O(1)-C(2)-C(1)
) 122.5(2), O(1)-C(2)-C(3) ) 119.1(2), C(1)-C(2)-C(3) )
118.5(2).
Figure 3. Ellipsoid representation of complex 11 (50% probability).
Selected bond lengths (Å) and angles (deg): Pd(1)-C(11) )
2.043(2), Pd(1)-N(1) ) 2.0753(17), Pd(1)-N(2) ) 2.1518(18),
Pd(1)-Cl(1) ) 2.3069(12), O(1)-C(17) ) 1.210(3), C(11)-C(12)
) 1.544(3), C(11)-C(15) ) 1.571(2), C(12)-C(13) ) 1.536(3),
C(12)-C(19) ) 1.548(3), C(13)-C(14) ) 1.530(3), C(14)-C(20)
) 1.541(3), C(14)-C(15) ) 1.550(3), C(15)-C(16) ) 1.528(3),
C(16)-C(17) ) 1.510(3), C(17)-C(18) ) 1.509(3), C(19)-C(20)
) 1.554(3), C(11)-Pd(1)-N(1) ) 93.56(7), N(1)-Pd(1)-N(2) )
78.42(6), C(11)-Pd(1)-Cl(1) ) 94.36(6), N(2)-Pd(1)-Cl(1) )
93.51(5), C(12)-C(11)-C(15) ) 103.09(14), C(13)-C(12)-C(11)
) 102.64(15), C(13)-C(12)-C(19) ) 100.61(17), C(11)-C(12)-
C(19))107.15(17),C(14)-C(13)-C(12))94.74(16),C(13)-C(14)-C(20)
)102.22(17),C(13)-C(14)-C(15))101.85(15),C(20)-C(14)-C(15)
) 107.97(16), C(16)-C(15)-C(14) ) 111.82(15), C(16)-C(15)-
C(11))115.50(15),C(14)-C(15)-C(11))102.45(14),C(17)-C(16)-C(15)
)114.15(16),O(1)-C(17)-C(18))120.55(19),O(1)-C(17)-C(16)
) 122.22(18), C(18)-C(17)-C(16) ) 117.22(18), C(12)-C(19)-
C(20) ) 103.54(16), C(14)-C(20)-C(19) ) 102.70(17).
reaction between DCl (from CDCl 3 ) and an hydroxo complex
(the impurity?) resulting from the hydrolysis of 13. In addition,
13 slowly decomposes in chlorinated solvents to give
[PdCl 2 (cod)]. The reaction of 1 with norbornadiene (1:1 molar
Figure 4. Ellipsoid representation of complex 13 (50% probability).
Selected bond lengths (Å) and angles (deg): Pd-C(1) ) 2.072(3),
Pd-C(5) ) 2.178(3), Pd-C(4) ) 2.193(3), Pd-Cl ) 2.3268(9),
Pd-C(9) ) 2.329(3), Pd-C(8) ) 2.358(3), O-C(2) ) 1.225(4),
C(1)-C(2) ) 1.467(5), C(2)-C(3) ) 1.501(5), C(4)-C(5) )
1.380(5), C(4)-C(11) ) 1.520(4), C(5)-C(6) ) 1.512(4), C(6)-C(7)
) 1.525(5), C(7)-C(8) ) 1.504(5), C(8)-C(9) ) 1.354(5),
C(9)-C(10) ) 1.499(4), C(10)-C(11) ) 1.539(5), C(1)-Pd-C(5)
) 89.66(13), C(1)-Pd-C(4)) 92.41(13), C(5)-Pd-C(4) )
36.81(12), C(1)-Pd-Cl ) 89.72(10), C(5)-Pd-C(9) ) 94.95(12),
C(4)-Pd-C(9))81.17(12),Cl-Pd-C(9))92.23(9),C(5)-Pd-C(8)
) 80.17(12), C(4)-Pd-C(8) ) 87.10(12), Cl-Pd-C(8) ) 95.09(9),
C(9)-Pd-C(8) ) 33.58(11).
ratio) in dry THF gave a mixture of products that could not be
separated.
Addition of 1,1-dimethyl allene (dma) to a solution of 1 in
acetonitrile (1.2:1 molar ratio) led to the isolation of the
dinuclear π-allyl complex [Pd{η 3 -CH 2 C[CH 2 C(O)Me]CMe 2 } 2 (µ-
Cl) 2 ](14, Scheme 2), resulting from the insertion of the allene
intothePd-Cbond.ThereactionofMe 4 N[Pt{CH 2 C(O)Me}Cl 2 (η 2 -
C 2 H 4 )] with dma gives instead the substitution product cis-
Me 4 N[Pt{CH 2 C(O)Me}Cl 2 (η 2 -H 2 CdCdCMe 2 )]. 27
Crystals apparently suitable for an X-ray crystallographic
study were obtained for 14, but although the structure shown
in Scheme 2 was established, a complete crystallographic
analysis was not possible. Disorder was so severe that, despite
repeated attempts and data collection at low temperature, no
satisfactory refinement was achieved. However, the composition
and the position of the organic ligand acting as η 3 -allyl were
established with certainty. η 3 -Allyl palladium complexes have
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