Microstructure Control of Ethene Homopolymers Through Tailored Ni,Pd(II) Catalysts - Late Transition Metal Polymerization Catalysis - page 50

Tab. 2.6 Selected bond lengths and angles of complex 11b, d .

Bond length [Å] Bond angles [ ]

11b
I1-Pd1 2.5731(11) N1-Pd1-P1 83.17(15)

I2-Pd1 2.6608(8) P1-Pd1-I1 90.22(5)

Pd1-N1 2.100(5) N1-Pd1-I2 94.63(14)

Pd1-P1 2.2298(18) I1-Pd1-I2 93.11(3)

11d
I1-Pd1 2.6531(13) N1-Pd1-P1 81.9(3)

I2-Pd1 2.5744(12) P1-Pd1-I2 92.18(8)

Pd1-N1 2.131(9) N1-Pd1-I1 94.7(2)

Pd1-P1 2.223(3) I2-Pd1-I1 92.14(4)

Tab. 2.7 Selected bond lengths and bond angles for 14b .

14b · 4(CCl 2 H) 2

Bond lengths [Å] Bond angles [ ]

Pd-P1 2.255(2) P2-Pd-P1 87.95(8)

Pd-P1 2.268(2) Cl2-Pd-Cl1 94.68(8)

Pd-Cl1 2.382(2)

Pd-Cl2 2.374(2) C30-P1-C21 106.8(4)

C30-P1-C1 100.5(4)

P1-C21 1.861(9) C21-P1-C1 113.0(4)

P1-C30 1.834(9)

P1-C1 1.867(9) C2-P2-C3 111.0(4)

C2-P2-C12 99.0(4)

P2-C3 1.840(9) C3-P2-C12 107.6(4)

P2-C2 1.833(9)

P2-C12 1.843(9)

We have further compared 14 c , d and [(DPPE)PdCl 2 ] after calculating the mean
planes of PdCl 2 P 2 sequence [55]. At least in the solid state the coordinated atoms
of [(DPPE)PdCl 2 ] show minimum deviations from the 5-atom plane (about
0.04 Å) and the shortest Pd-P bond lengths (2.233(2) and 2.227(2) Å) of all com-
plexes. The 2-isopropyl substituted compound 14 c exhibits moderate deviations
from planarity (about 0.13-0.14 Å) and longer Pd-P bond lengths (2.256(2) and
2.252(2) Å). 2,4,6-Isopropyl substituted 14d reveals the largest deviation from the
mean plane (approximately 0.20 Å) and the longest Pd-P bonds in general
(2.278(10) and 2.3041(11) Å). In 14b the deviations of the PdCl 2 P 2 unit from the
square planar coordination plane, the P1-Pd-P2 angle and the Pd-P bond lengths
are between those found for 14 c and 14d . In each compound the Pd atom itself
is approximately in the five atom mean plane. The distortion of coordinated