Linear Cu^I₂Pd⁰, Cu^IPd⁰₂, and Ag^I₂Pd⁰ Metal Chains Supported by Rigid N,N′‐Diphosphanyl N‐Heterocyclic Carbene Ligands and Metallophilic Interactions

Abstract

occasion of his70th birthday and for his outstanding contributionst oc luster chemistry Abstract: Selective copper(I)t op alladium(0) transmetallation of P-donors from the rigid N,N'-diphosphanyl-imidazol-2-ylidene C 3 H 2 [NP(tBu) 2 ] 2 (PC NHC P)w as observed when known [Cu 3 (m 3 -PC NHC P,kP,kC NHC ,kP) 2 ](OTf) 3[1] wasr eactedw ith [Pd(PPh 3 ) 4 ]. When 1.2 equivalents of [Pd(PPh 3 ) 4 ]w as used, the product [Cu 2 Pd(m 3 -PC NHC P,kP, kC NHC ,kP) 2 ](OTf) 2 (2(OTf) 2 ) was obtained, which features aC u I -Cu I -Pd 0 chain anda ppears to be the first linear heterotrinuclear complex with d 10 -d 10 interactions between Pd 0 and Cu I .W hen the Cu 3 precursor was reacted with 3.0 equivalents of [Pd(PPh 3 ) 4 ], the complex [CuPd 2 (m 3 -PC NHC P,kP, kC NHC ,kP) 2 ](OTf) 2 (3(OTf) 2 )w as obtained,w hich,o nt he basis of magnetic measurements, DFT calculations, and computed nuclear shieldings, wasf ormulated as containing aP d 0 -Cu I -Pd 0 chain with an electron hole delocalizedo ver the whole cation, including the metal chain. Similarly,s electivet ransmetallation of the P-donors in [Ag 3 (m 3 -PC NHC P,kP,kC NHC ,kP) 2 ](OTf) 3 from silver to palladium (originating from [Pd(PPh 3 ) 4 ]) gave the linear chain [Ag 2 Pd(m 3 -PC NHC P,kP, kC NHC ,kP) 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 )f ormulation. Upon standing in solution, 5(OTf) 2 transformed to 6(OTf) 2 ,t he regioisomer of 5(OTf) 2 in which the Pd centerh as migrated to the central positiono fa n Ag I -Pd 0 -Ag I chain. Prolonged standing in CH 2 Cl 2 or by reaction with [PtCl 2 (NCMe) 2 ]c onverts complex 6(OTf) 2 to the Ag I /Pd II complex [Ag 2 PdCl 2 (m 3 -PC NHC P,kP, kC NHC ,kP) 2 ](OTf) 2 (7(OTf) 2 ). The structurald ata of 2(OTf) 2 , 3(OTf) 2 ,a nd 7(OTf) 2 establish significant heterometallophilic interactions.[a] Dr.and New address:UniversitØ de Strasbourg,C NRS Institut de biologie molØculaire des plantes 12 rue du gØnØralZ immer 67084 Strasbourg cedex(France) [g] Prof. A. A. Danopoulos Institute for Advanced Study, USIAS, UniversitØ de Strasbourg( France) [h] Prof. A. A. Danopoulos New address:Laboratory of Inorganic Chemistry Nationaland Kapodistrian University of Athens,P anepistimiopolis Zografou Athens GR 15771 (Greece) Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.org/10.1002/chem.201801170. It contains experimental detailsand computational studies with the coordinates of the computed structures of cations 2* and 3* and cations 7* vac and 7* MeCN ;crystal structure determinations of 2(OTf) 2 ·CH 2 Cl 2 , 3(OTf) 2 ,a nd 7(OTf) 2 with crystal data and refinementdetails; magnetic data for 3(OTf) 2 ;X-ray absorption spectroscopy studieso n[ Pd-Cu-Pd(m 3 -PC NHC P) 2 ](OTf) 2 , 3(OTf) 2 ;main interatomic dis...

Alternative Transformations of N-Heterocyclic Carbene Complexes of the Group 11 Metals in Transmetalation Reactions (A Review)

“…The known reactions of transmetalation from NHC-Ag(I) to Pd 0 [101][102][103][104][105][106][107][108][109][110][111][112][113] has occurred with preservation of the palladium oxidation state. It has been shown by Peters et al [114] that the reaction of bimetallic complexes 48 and 49 with 0.6 eq.…”

“…However, [105] has provided an example where the NHC-Pd(0) complex 62 isolated upon the transmetalation has been completely oxidized and transformed in the NHC-Pd(II) chloride complex 63 during keeping in a solution in MeCN-CH 2 Cl 2 or in MeCN in the presence of PtCl 2 (NCPh) 2 (Scheme 19), the oxidation state of the Ag(I) centers in the complex being preserved. In view of the structure of the considered Pd(0) complexes, radical or S N 2 mechanism of the oxidative addition [116] of CH 2 Cl 2 with further transformations has been suggested.…”

“…Another example of selective transmetalation has been described in [105]. The treatment of the phosphine carbene complex of Cu(I) 101 with 1.2 eq.…”

Photoluminescence control by atomically precise surface metallization of C-centered hexagold(i) clusters using N-heterocyclic carbenes

“…1). [45][46][47] As a result, a tetrahedral form of [(C)(Au I -BIPc 2 ) 6 Ag I 4 (CH 3 CN) 2 ](BF 4 ) 6 (4), a CAu I 6 Ag I 4 -type cluster, was obtained in which the outer shell part composed of (BIPc 2 ) 6 Ag I 4 covered the octahedral CAu I 6 cluster (Scheme 1). By introducing an additional ligand in the wingtip group of the carbene ligand and increasing the number of Ag I ions bound to CAu I 6 , strong red phosphorescence with a QY of 0.40 and a lifetime of 1.41 ms was observed in CH 2 Cl 2 , both of which were signicantly improved compared to cluster 3.…”

Exploring the Coordination Properties of Phosphonium‐Functionalized N‐Heterocyclic Carbenes Towards Gold

“…To date, several examples of backbone functionalized NHCs that feature neutral (like for example À OR, À NR 2 , À PR 2 , À SR, À SeR groups), anionic (like À O À , À NR À , À S À , À SO 3 À , À COO À groups) or even cationic (like À NR 3 + , À PR 3 + groups) moieties have been described. [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26][27] The exploitation of the second functionality allows for example to obtain polynuclear complexes, [28,29] the anchoring of the complex to polymers, [30] surfaces or nanoparticles. [31] This also increases the robustness of the whole molecular system in the case of catalytic activity.…”