Palladium(II)-Komplexe des 1,1,3,3,5,5-Hexakis(dimethylamino)-λ5-[1,3,5]triphosphinins

Heckmann, Gernot; Plank, Stefan; Schwarz, W.; Fluck, E.

doi:10.1002/(sici)1521-3749(199905)625:5<773::aid-zaac773>3.3.co;2-8

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“…Cyclic bis-and tris-(P-ylides) also reacted with [PdCl 2 (NCPh) 2 ] to afford the C,C-cyclic complexes 43 a, [48] 43 b, [44] 43 c, [44] and 43 d, [49] The crystal structures of 43 a and 43 d were determined by X-ray diffraction studies (Scheme 34).…”

Section: Systems Based On the Coordination Of Bis-ylidesmentioning

confidence: 99%

Chasing C,C‐Palladacycles

Garcı́a-López

Saura‐Llamas

2021

Eur J Inorg Chem

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The different approaches for the synthesis of C,C-palladacycles are reviewed in this manuscript. These species hold a bidentate ligand that chelates the Pd atom through two C-donor moieties. Their relevance is closely related to the fact that they are intermediates in many palladium-catalyzed transformations. Furthermore, some of them have been used as efficient catalyst in cross coupling reactions. The review is structured according to the different strategies that have been employed to achieve the synthesis of the C,C-palladacycle derivatives, starting with those involving one elemental step (such as the oxidative addition of strained CÀ C bonds to Pd(0) or the transmetalation reactions between organometallic reagents and Pd(II) precursors), and continuing with more complex processes, where at least two elementary steps of Pd chemistry are involved (for example, carbometalation of alkenes followed by a CÀ H activation process). A final section highlights some aspects of synthetic methodologies based on Pd catalysis in which one or several C,C-palladacyclic intermediates are involved.Lenarda et al. synthesized the first reported four-membered C,C-palladacycles 1 a and 1 b in 1972, [5] via the oxidative addition of 1,1,2,2-tetracyanocyclopropane to [Pd(PPh 2 R) 4 ] (R = Ph; Me) (Scheme 1). The reaction occurred with the CÀ C bond cleavage of the highly strained ring and oxidative addition of the two resulting fragments to Pd(0).

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