Synthesis, Spectroscopy, and Solid-State Structural Characterization of the Hexanuclear Copper Macrocycle [Cu6Cl6(μ-PCHP)6]

Novel octanuclear copper(i) metallomacrocycles and their transformation into hexanuclear 2-dimensional grids of copper(i) coordination polymers containing cyclodiphosphazanes, [(μ-NtBuP)2(NC4H8X)2] (X = NMe, O)

“…8 The fascinating photoluminescent characteristics of these metal assemblies of closed shell d 10 metal ions have been demonstrated via ligand supported 9 or un-supported 10 metal-metal interactions. Among the coinage metals, high nuclearity metallomacrocycles are quite common with gold 11 but much less common for copper 12 and silver. 13 Copper(I) halides readily form complexes with soft and hard donor atoms in which the coordination number at the metal center can be two, three or four.…”

Copper(I) Complexes Containing PCP Ligand Catalyzed Hydrogenation of Carbon Dioxide to Formate under Ambient Conditions

“…The Cu–P bond lengths are significantly shorter than those of reported complexes based on the ligand 1,3-bis­[(di- tert -butylphosphino)­methyl]­benzene . The average P–C methylene bond lengths in complexes 1 and 3 are 1.857(13)–1.866(14) and 1.844(11)–1.848(11) Å, respectively, which are shorter than that of the PCP t ‑Bu ligand (the P–C methylene bond length is 1.870 Å) . This bond shortening is accompanied by a change in the P–C methylene –C phenyl angle, from 114.5° in the free ligand to 113.8(9)–118.4(10)° (P–C methylene –C phenyl angles for 1 C(1)–C(7)–P(2) 113.8(9), C(5)–C(16)–P(1) 118.4(10), C(29)–C(40)–P(3) 115.8(9), C(25)–C(31)–P(4) 116.9(10); P–C methylene –C phenyl angles for 3 C(1)–C(7)–P(1) 117.3(7), C(5)–C(16)–P(2) 116.5(8)).…”

“…28 The average P−C methylene bond lengths in complexes 1 and 3 are 1.857(13)−1.866( 14) and 1.844(11)−1.848(11) Å, respectively, which are shorter than that of the PCP t-Bu ligand (the P−C methylene bond length is 1.870 Å). 25 This bond shortening is accompanied by a change in the P−C methylene −C phenyl angle, from 114.5°in the free ligand to 113.8(9)−118.4( 10 8)). The two Cu− Cl as well as Cu−I bond lengths are asymmetrical.…”

“…24 Recently other interesting systems with 1,3-bis[(di-tertbutylphosphino)methyl]benzene copper(I) complexes have attracted our interest because the limited structural and application potential for such systems have been investigated. A previous literature report suggests that CuCl:PCP t-Bu (1:2) yielded the hexanuclear complex [Cu 6 Cl 6 (μ-PCHP) 6 ], 25 but no structural reports dealing with CuX:PCP t-Bu (1:1/1:2) (X = Cl, Br, I, CN, SCN) have been published to date. With this perspective, we therefore set out to explore the coordination of the neutral 1,3-bis [(di-tert-butylphosphino)methyl]benzene ligand with Cu(I) species.…”

Cyclodiphosphazanes with functionalities: Synthesis, reactivity and transition metal chemistry

“…The compounds 45 and 46 are 24-membered metallamacrocycles containing P 2 N 2 rings and rhombic [Cu 2 (l-I) 2 ] units in an alternating fashion. These are rare examples of copper(I) macrocycles containing phosphorus based ligands; the only other known phosphorus containing CuI complex is a hexanuclear complex [Cu 6 Cl 6 ( t Bu 2 PCH 2 C 6 H 4 CH 2 P t Bu 2 ) 6 ] containing six tricoordinated Cu I ions linked via a bisphosphine, as shown in Chart 5[38].Interaction of octanuclear complexes 45 or 46 with 4,4 0 -bipyridine in 1:2 molar ratio gave hexanuclear 2D grid-like polymers [{[(4,4 0 -bpy) 2 Cu 2 (l-I){l-( t BuNPNC 4 H 8 X) 2 ][Cu 2 (l-I){l-( t BuNPNC 4 H 8 -X) 2 }(I) 2 ]} 1 ] (47, X = O; 48, X = NMe) as yellow crystalline complexes (Scheme 13). The molecular structure consists of interesting cationic 2-dimensional grid-like coordination polymers [{[(4,4 0 -bpy) 2 Cu 2 (l-I){l-( t BuNPNC 4 H 8 X) 2 }} 1 ] + containing [Cu 2 (l-I){l-( t BuNPNC 4 H 8 X) 2 }(I) 2 ]} 1 ] À anions trapped inside the hexanuclear metallamacrocyclic units as shown in Chart 6[7].…”