A variable temperature ³¹P NMR study of 9-30 atom macrocylic rings of silver(I) with long chain diphosphines

From Short-Bite Ligand Assembled Ribbons to Nanosized Networks in Cu(I) Coordination Polymers Built Upon Bis(benzylthio)alkanes (BzS(CH2)nSBz; n = 1–9)

“…The coordination chemistry of long chain diphosphine ligands of type R 2 P­(CH 2 ) n PR 2 ( n ≥ 5) has intrigued coordination chemists since the 1970s as their flexibility induces various coordination modes such as η 1 -mondentate, chelating, or trans -spanning upon complexation onto transition metals. − For instance, selected examples of discrete molecular complexes and large macrocycles ligated by with 1,8-bis­(diphenylphosphino)­octane (dppo) include the monosubstituted [(η 5 -indenyl)­Fe­(CO) 2 (η 1 -dppo)]­[BF 4 ], dimeric [{(η 5 -indenyl)­Fe­(CO) 2 } 2 (μ-dppo)] 2 [BF 4 ] 2 , dinuclear [(μ-bpym)­Cu 2 (μ-dppo) 2 ]­[BF 4 ] 2 (bpym = 2,2‘-bipyrimidine), and macrocyclic species cis -[Mo 2 (CO) 8 (μ-dppo) 2 ]. − However, Ph 2 P­(CH 2 ) 8 PPh 2 has also been used as an assembling ligand to construct polymers networks such as one-dimensional (1D) [IAu­(μ-dppo)­AuI] n , [ClAu­(μ-dppo)­AuCl] n , and 1D [Ag 12 (SCy) 12 (μ-dppo)] n . , Note that with CuI and Ph 2 P­(CH 2 ) n PPh 2 ( n = 1, 2, 3, 4, 5, 6), only discrete zero-dimensional (0D) complexes are formed. − Chart presents some selected examples of such (CuI) n clusters as well as some molecular metal complexes and CPs ligated by dppo.…”

“…1−8 For instance, selected examples of discrete molecular complexes and large macrocycles ligated by with 1,8-bis(diphenylphosphino)octane (dppo) include the monosubstituted [(η5 -indenyl)Fe-(CO) 2 (η 1 -dppo)][BF 4 ], dimeric [{(η 5 -indenyl)Fe(CO) 2 } 2 (μdppo)] 2 [BF 4 ] 2 , dinuclear [(μ-bpym)Cu 2 (μ-dppo) 2 ][BF 4 ] 2 (bpym = 2,2'-bipyrimidine), and macrocyclic species cis-[Mo 2 (CO) 8 (μ-dppo) 2 ]. 9−11 However, Ph 2 P(CH 2 ) 8 PPh 2 has also been used as an assembling ligand to construct polymers networks such as one-dimensional (1D) [IAu(μ-dppo)AuI]…”