Full Paper
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solved by direct methods (SHELXS-97) and refined by full-matrix
least-squares techniques against F2 (SHELXL-97).[35] The non-
hydrogen atoms were refined anisotropically {except for the par-
tially occupied atoms of the solvent in [Rh(DIPAMP)(Ph)(I)]2[BF4]2}.
The hydrogen atoms were placed in theoretical positions {except
for OH in the coordinated MeOH in [Rh(DIPAMP)(Ph)(Cl)(MeOH)]BF4}
and were refined by using the riding model. Contributions of
solvent molecules were removed from the diffraction data for
[Rh(DIPAMP)(Ph)(I)]2(BF4)2 with PLATON/SQUEEZE. Crystal data for
[Rh(DIPAMP)(Ph)(Cl)(MeOH)]BF4: C35H37BClF4O3P2Rh, orthorhombic
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space group P212121,
a
=
8.5169(5),
b
=
19.6354(11),
c
=
=
=
20.5238(12) Å, V = 3432.3(3) Å3, T = 150(2) K, Z = 4, ρcalcd.
1.534 g cm–3, μ(Mo-Kα) = 0.725 mm–1. 28678 total data, Θmax
26.00°. R = 0.0478 for 6755 data with I > 2σ(I) of 5663 unique data
and 430 refined parameters. The final R1 value was 0.0642 (all data).
The final wR(F2) value was 0.1149 (all data). The goodness of fit on
F2 was 1.099. Flack parameter = 0.026(19). Crystal data for [Rh-
[8]
[9]
(DIPAMP)(Ph)(Br)(MeOH)]BF4·MeOH:
C35H37BBrF4O3P2Rh·MeOH,
orthorhombic space group P212121, a = 8.9599(3), b = 17.8978(5),
c = 22.7985(7) Å, V = 3656.02(19) Å3, T = 150(2) K, Z = 4, ρcalcd.
=
=
1.579 g cm–3, μ(Mo-Kα) = 1.706 mm–1. 50876 total data, Θmax
29.62°. R = 0.0207 for 10258 data with I > 2σ(I) of 9670 unique data
and 448 refined parameters. The final R1 value was 0.0233 (all data).
The final wR(F2) value was 0.0475 (all data). The goodness of fit on
F2 was 1.005. Flack parameter = 0.023(3). Crystal data for [Rh-
(DIPAMP)(Ph)(I)]2(BF4)2·0.5MeOH:
C68H66B2F8I2O4P4Rh2·0.5MeOH,
trigonal space group P2121, a = 15.9481(11), b = 15.9481(11), c =
[10]
27.5493(19) Å, V = 6068.2(9) Å3, T = 150(2) K, Z = 6, ρcalcd.
=
=
1.411 g cm–3, μ(Mo-Kα) = 1.309 mm–1. 86809 total data, Θmax
[11]
[12]
[13]
25.24°. R = 0.0251 for 8598 data with I > 2σ(I) of 7902 unique data
and 413 refined parameters. The final R1 value was 0.0393 (all data).
The final wR(F2) value was 0.0932 (all data). The goodness of fit on
F2 was 1.019. CCDC 1499320 {for [Rh(DIPAMP)(Ph)(Cl)(MeOH)]BF4},
1499321 {for [Rh(DIPAMP)(Ph)(Br)(MeOH)]BF4}, and 1499319 {for
[Rh(DIPAMP)(Ph)(I)]2[BF4]2} contain the supplementary crystallo-
[14]
Keywords: Oxidative addition · Rhodium · UV/Vis
spectroscopy · C–C coupling · Product inhibition
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Eur. J. Inorg. Chem. 2017, 2040–2047
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