Synthese und Molekülstruktur der Cu₄P₈‐Käfigverbindung [Cu₄(P₄Ph₄)₂(PCyp₃)₃]

Abstract

Lineare und cyclische Oligophosphanidanionen (P n R n ) 2À (n = 2-4) und cyclo-(P m R mÀ1 ) À (m = 3-5) sind attraktive Liganden, die eine Vielzahl von potenziellen Koordinationsmodi aufweisen. Die linearen dianionischen (P n R n ) 2À -Spezies wurden zuerst von Issleib und Mitarbeitern durch die Reduktion von Cyclooligophosphanen cyclo-(P n R n ) mit Alkalimetallen erhalten.[1] Die Kettenlänge der (P n R n ) 2À

Coordination Chemistry of the cyclo‐(P5tBu4)− Ion: Monomeric and Oligomeric Copper(I), Silver(I) and Gold(I) Complexes

“…[12] The Cu À P phosphane bond lengths of 231.3(2) pm (Cu1 À P6) and 227.1(2) pm (Cu1 À P7) in 3 are % 6 pm longer than in other copper(I) phosphane complexes. [11,12] This phenomenon is not observed in 4, in which the Cu À P phosphane bond lengths are 221.0(1) (Cu1 À P6) and 223.3(1) pm (Cu2ÀP7). The four PÀP distances in the P 5 ring are in the range from 221.0(2) to 222.2(2) pm in 3 and from 220.0(2) to 221.8(2) pm in 4, which are typical values for PÀP single bonds.…”

“…Keywords: copper · gold · P ligands · phosphorus · silver 2-4) [10] and have reported the synthesis of the first copper(I) oligophosphanide complex [Cu 4 A C H T U N G T R E N N U N G (P 4 Ph 4 ) 2 A C H T U N G T R E N N U N G (PCyp 3 ) 3 ], which was obtained from the reaction of two equivalents of [CuCl-A C H T U N G T R E N N U N G (PCyp 3 ) 2 ] with one equivalent of [Na 2 A C H T U N G T R E N N U N G (thf) 5 A C H T U N G T R E N N U N G (P 4 Ph 4 )]. [11] Inspired by this result, we have now studied the reactivity of [NaA C H T U N G T R E N N U N G {cyclo-A C H T U N G T R E N N U N G (P 5 tBu 4 )}] (1) with copper(I), silver(I) and gold(I) halides. Although, numerous oligonuclear copper(I) and silver(I) phosphanido complexes are known [12] oligonuclear gold(I) phosphanides with six-, eight-and twelve-membered Au n P n rings have been reported only recently.…”

The unusual coordination chemistry of phosphorus-rich linear and cyclic oligophosphanide anions

“…One of the first interesting results was obtained with copper(I) compounds [46]. While the reaction of CuCl with [Na 2 (thf) 5 (P 4 Ph 4 )] (32) or K 2 (P 4 Bu t 4 ) led only to a black precipitate consisting of elemental copper, NaCl and the cyclophosphanes cyclo-(P n Ph n ) (n = 4-6) or cyclo-(P 4 Bu t 4 ), respectively, the reaction of [CuCl(PCyp 3 ) 2 ] (Cyp = cyclo-C 5 H 9 ) with [Na 2 (thf) 5 (P 4 Ph 4 )] (32) yielded the tetranuclear copper(I) complex [Cu 4 (P 4 Ph 4 ) 2 (PCyp 3 ) 3 ] (47) (Fig.…”

“…3(6) 296.0 (6) [Na2(thf)5(P4Ph4)] (32) 216.6(1) 289.2(2) AA BB [34] 220.7(2) 290.1 (2) [Na2 ( AA BB X c [40] 219.8 (2) 228.5 (2) [K (18-crown[6])(P4HMes4)] (45) 215.2(2) 336.4 (2) AA BB X c [40] 220.2(4) 227. 6(2) [K(tmeda){Ga(P4Ph4)(DAB)}] (46) 219.4 (2) 238.2 (2) [46] 220.0(3) 227.1(2) 220. 6(3) 228.1(2) 221.…”

[Li(tmeda)2][cyclo-(P5But4)]: An unusual ion-separated lithium oligophosphanide

“…1b) and thus results in a ''naked'' [cyclo-(P 5 Bu t 4 )] À anion (Li(1)Á Á ÁP(1) 494.0(6) pm). This type of anionic twocoordinate phosphorus atom is typical in metal complexes of white phosphorus (see for example [13] and references therein), but rare for linear or cyclic oligophosphanides [2,3,7,9,14]. Only a few examples display an ion-separated structure, such as [K(18-crown-6)(thf) 2 ][P 4 HMes 4 ] (Mes = 2,4,6-Me 3 C 6 H 2 ), in which the potassium cation is coordinated by 18-crown-6 and two THF molecules [3a], Table 1 Comparison of simulated 31 P{ 1 H} NMR data for M[cyclo-(P 5 Bu t 4 )] (M = Li, Na, K).…”