Unexpected Reactivities of Cu₂(diphosphine)₂ Complexes in Alcohol:  Isolation, X-ray Crystal Structure, and Photoluminescent Properties of a Remarkably Stable [Cu₃(diphosphine)₃(μ₃-H)]²⁺ Hydride Complex

Abstract

Treatment of [Cu2(dcpm)2]Y2 (dcpm = bis(dicyclohexylphosphino)methane, Y = ClO4-, BF4-, PF6-, CF3SO3-) with refluxing MeOH in the presence of KOH afforded hydride complexes [Cu3(dcpm)3(mu3-H)]Y2 (1) in about 85% yield. Refluxing [Cu2(dcpm)2](PF6)2 with MeOH in the presence of NH3.H2O and air gave a carboxylate complex [Cu2(dcpm)2(O2CCH2OH)]PF6 (2) in 40% yield. All of the complexes 1 and 2 have been characterized by X-ray crystallography. The Cu3 cores in 1 are almost perfectly shielded by the dcpm ligands. Intense photoluminescence was observed for 1 both in the solid state and in solution.

Synthesis, Structural Characterization, and Gas-Phase Unimolecular Reactivity of the Silver Hydride Nanocluster [Ag3((PPh2)2CH2)3(μ3-H)](BF4)2

“…In the structurally related d 10 nanocluster, [Cu 3 (μ 3 -H)-(dcpm) 3 ] 2+ [dcpm = bis(dicyclohexylphosphino)methane], a resonance at ∼2.2 ppm was attributed to the hydride because of the fact that it was a septet with 2 J P−H = 16 Hz. 19 The chemical (4) a Distances were determined by X-ray diffraction except those involving deuterium, which were determined by neutron diffraction. (2)…”

“…It is not clear whether this is due to the fact that decomposition of the tetrafluoroborate anion releases F − , which is a more potent gas-phase base than Cl − , 23 or whether it is due to the fact that Cl remains bound to the Ag 3 core in [Ag 3 (D)(Cl)L 3 ] + , while [Ag 3 (D)(BF 4 )L 3 ] + and [Ag 2 (BF 4 )L 2 ] + have contact ion-pair structure(s). ; dcpm = bis(dicyclohexylphosphino)-methane] 19 and [Ag 3 (μ 3 -CCAr)(dppm) 3 ](BF 4 ) 2 (Ar = Ph, pMeOC 6 H 5 , p-O 2 NC 6 H 5 ), 24 and highlights the value of neutron diffraction for the definitive determination of the structures of metal hydrides. In the present example, the addition of borohydride expands the nuclearity of the clusters formed, leading to a silver(I) hydride complex and not a mixed-valent silver(0/I) cluster.…”

Facile Insertion of Carbon Dioxide into Cu2(μ‐H) Dinuclear Units Supported by Tetraphosphine Ligands

“…2.882 ), [11] thus indicating no direct metal À metal bonding interaction in the Cu 2 A C H T U N G T R E N N U N G (m-H) unit. The hydride was determined by difference Fourier syntheses at Cu À H = 1.62 and Cu-H-Cu = 1208.…”

“…(L= N-heterocyclic carbene (NHC), [9a] cyclic alkylA C H T U N G T R E N N U N G (amino)carbene (CAAC)), [10] [Cu 3 A C H T U N G T R E N N U N G (m 3 -H)(Cy 2 PCH 2 PCy 2 ) 3 ] 2 + , [11] and [ [12] have been reported. …”

A novel triply bridged dinuclear four-coordinate copper(I) complex with sterically bulky bis(dicyclohexylphosphino)methane ligand

“…Some novel copper(I) complexes with paa and dcpm ligands have A novel triply bridged dinuclear four-coordinate Copper(I) Complex with sterically bulky bis(dicyclohexylphosphino)methane ligand also been synthesised. To the best of our knowledge, even though the copper(I) complexes with dcpm were extensively investigated [17][18][19], few tetra-coordination copper(I) complexes with dcpm ligands were reported so far due to the steric bulkiness and severe distorting involving some of the carbon atoms of the dcpm ligand. In this paper, the synthesis of a novel tetra-coordination Cu 2 (µ-paa)(µ-dcpm) 2 (BF 4 ) 2 is reported and its crystal structure and optical properties are studied in detail.…”