75. Scheetz,
P. M.; Blank, N. F.; Gibbons, S. K.; Glueck, D.
S.; Rheingold, A. L. Oxidative Addition of
Methylene Chloride to Me-DuPhos Complexes of
Palladium and Rhodium. Inorg. Chim. Acta2018, 483, 111-115.
Abstract
Oxidative addition of methylene chloride to Pd((R,R)-Me-DuPhos)(L)
(1–3; L = P(t-Bu)3,
PCy3, or trans-stilbene) gave Pd((R,R)-Me-DuPhos)(CH2Cl)(Cl)
(4). Treatment of [Rh(COD)(Cl)]2 with
(R,R)-Me-DuPhos at low temperature in THF or CH2Cl2
afforded [Rh((R,R)-Me-DuPhos)(Cl)]2 (5).
At room temperature, these reactions also gave the byproduct [Rh((R,R)-Me-DuPhos)2][Cl],
which was prepared independently as the BF4 salt 6.
When 5 was generated in CH2Cl2,
oxidative addition of both CCl bonds yielded the bridging carbene complex (Rh((R,R)-Me-DuPhos)(Cl))2(µ-Cl)2(µ-CH2)
(8). Both 6 and 8
were crystallographically characterized.
