In:
Chemistry – A European Journal, Wiley, Vol. 24, No. 35 ( 2018-06-21), p. 8787-8796
Abstract:
Selective copper(I) to palladium(0) transmetallation of P‐donors from the rigid N , N ′‐diphosphanyl‐imidazol‐2‐ylidene C 3 H 2 [NP( t Bu) 2 ] 2 ( PC NHC P ) was observed when known [Cu 3 (μ 3 ‐ PC NHC P ,κ P ,κ C NHC ,κ P ) 2 ](OTf) 3 was reacted with [Pd(PPh 3 ) 4 ]. When 1.2 equivalents of [Pd(PPh 3 ) 4 ] was used, the product [Cu 2 Pd(μ 3 ‐ PC NHC P ,κP,κC NHC ,κP) 2 ](OTf) 2 ( 2 (OTf) 2 ) was obtained, which features a Cu I –Cu I –Pd 0 chain and appears to be the first linear heterotrinuclear complex with d 10 –d 10 interactions between Pd 0 and Cu I . When the Cu 3 precursor was reacted with 3.0 equivalents of [Pd(PPh 3 ) 4 ], the complex [CuPd 2 (μ 3 ‐ PC NHC P ,κP,κC NHC ,κP) 2 ](OTf) 2 ( 3 (OTf) 2 ) was obtained, which, on the basis of magnetic measurements, DFT calculations, and computed nuclear shieldings, was formulated as containing a Pd 0 –Cu I –Pd 0 chain with an electron hole delocalized over the whole cation, including the metal chain. Similarly, selective transmetallation of the P‐donors in [Ag 3 (μ 3 ‐ PC NHC P ,κ P ,κ C NHC ,κ P ) 2 ](OTf) 3 from silver to palladium (originating from [Pd(PPh 3 ) 4 ]) gave the linear chain [Ag 2 Pd(μ 3 ‐ PC NHC P ,κP,κC NHC ,κP) 2 ](OTf) 2 ( 5 (OTf) 2 ), which on the basis of NMR spectroscopy comprises an Ag I –Ag I –Pd 0 metal core. However, X‐ray diffraction data collected on various samples of 5 (OTf) 2 were modeled with 50:50 metal disorder at the terminal positions, corresponding to a (Ag I /Pd 0 )–Ag I –(Ag I /Pd 0 ) formulation. Upon standing in solution, 5 (OTf) 2 transformed to 6 (OTf) 2 , the regioisomer of 5 (OTf) 2 in which the Pd center has migrated to the central position of an Ag I –Pd 0 –Ag I chain. Prolonged standing in CH 2 Cl 2 or by reaction with [PtCl 2 (NCMe) 2 ] converts complex 6 (OTf) 2 to the Ag I /Pd II complex [Ag 2 PdCl 2 (μ 3 ‐ PC NHC P ,κP,κC NHC ,κP) 2 ](OTf) 2 ( 7 (OTf) 2 ). The structural data of 2 (OTf) 2 , 3 (OTf) 2 , and 7 (OTf) 2 establish significant heterometallophilic interactions.
Type of Medium:
Online Resource
ISSN:
0947-6539
,
1521-3765
DOI:
10.1002/chem.201801170
Language:
English
Publisher:
Wiley
Publication Date:
2018
detail.hit.zdb_id:
1478547-X
