Cu+ and Cu0 centers are found in the mixed valent compounds [Cu32As30(dppm)8] (structure shown in the picture) and [Cu26Te12(PEt2Ph)12] which formally contain a Cu3230+ or a Cu2624+ cluster core, respectively. Calculations of the electronic band structure show that a localization of the formal oxidation states is impossible. Both compounds contain a central Cu6 octahedron. The short Cu−Cu bonds do not result from d10–d10 interactions. dppm=methylene[(diphenyl)phosphine].

Inhaltsiibersicht. Bei Umsetzungen von Pb12 mit NaI in polaren organischen Losungsmitteln entstehen Iodoplumbatkomplexe unterschiedlicher Zusammensetzungen und Strukturen, die durch Kristallisation mit groRen Kationen isoliert werden konnen. [Na3(OCMez)121[Pb41,,(OCMe2)1 3, (Ph4P)2[Pb511~I 4 und (Ph4P)4[Pb15134(dmf)6] 7 enthalten eindimensional unendliche Anionen, die aus flachen-bzw. kantenverknupften Pb1,-oder PbI&Oktaedern (L = Aceton, DMF) aufgebaut sind.[Na3(OCMe2),2][Pb4111(OCMe2)] 3: Raumgruppe PI (Nr. I), a = 1120,3(5), b = 1265,3(6), c = 1608,3(8)pm, 01 = 74,64(4), p = 70,40(4), y = 85,24(4)", V = 2071(2) * 106pm3;(Ph4P),[Pb5112] 4: Raumgruppe C2/c (Nr. 15), a = 787,00(10), b = 2812,0(5), c = 3115,9(5) pm, p = 96,240 (13)", V = 6885(2) . 106pm3; (Ph,P),[Pbi51~4(dmf)6] 7: Raumgruppe P2Jn (Nr. 14), a = 2278,8(4), b = 1782,6(3), c = 2616,8(4) pm, / 3 = 114,432(13)", V = 9678(3) * 106pm3. Abstract. Reactions of PbIz with NaI in polar organic solvents followed by crystallization with large cations yield iodoplumbate complexes with various compositions and structures. [Na3(OCMe2)lzl [Pb4111(OCMe2)1 3, (Ph4P)2[Pb51121 4 and (Ph4P)4[Pb15134(dmf>6] 7 contain one-dimensional infinite anionic chains of face-or edge-sharing Pb16 or Pb15L (L = acetone, DMF) octahedra. [Na3(OCMe2)12] [Pb411,(OCMe2)] 3: Space group PI (No. I), a = 1120.3(5), b = 1265.3(6), c = 1608.3(8) pm, 01 = 74.64(4), p = 70.40(4), y = 85.24(4)", V = 2071(2) . 106pm3; (Ph4P)2[Pb511z] 4: Space group C2/c (No. 15), a = 787.00(10), b = 2812.0(5), c = 3115.9(5) pm, p = 96.240(13)", V = 6885(2) * 106pm3; (Ph4P)4[Pb15134(dmf)6] 7: Space group P2,/n (No. 14), a = 2278.8(4), b = 1782.6(3), c = 2616.8(4)pm, p = 114.432(13)", V = 9678(3) -106pm3.

Inhaltsübersicht. Die Reaktion von CuCl, LiAs(SiMe 3 ) 2 und dppb (Bis(diphenylphosphino)butan) führt zur Bildung ionischer Cluster-Komplexe. In Abhängigkeit von den Reaktionsbedingungen lassen sich [Cu 8 As 3 (AsSiMe 3 ) 2 (dppb) 4 ] ϩ [Cu{As 2 (SiMe 3 ) 2 }-{As 4 (SiMe 3 ) 4 }] Ϫ (1) und [Cu 8 As 3 (AsSiMe 3 ) 2 (dppb) 4 ] ϩ -Abstract. The reaction of CuCl, LiAs(SiMe 3 ) 2 and dppb (Bis(diphenylphosphino)butane) leads to the formation of ionic cluster complexes. Depending on the reaction conditions one can isolate [Cu 8 As 3 (AsSiMe 3 ) 2 (dppb) 4 ] ϩ [Cu{As 2 (SiMe 3 ) 2 }{As 4 (SiMe 3 ) 4 }] Ϫ (1) and [Cu 8 As 3 (AsSiMe 3 ) 2 (dppb) 4 ] ϩ [Cu{As(SiMe 3 ) 2 } 2 ] Ϫ (2). The same reaction of CuCl, dppm (Bis(diphenylphosphino)methane)

Aus Cu+‐ und Cu0‐Zentren bestehen die gemischtvalenten Verbindungen [Cu32As30(PPh2CH2PPh2)8] (Struktur siehe Bild) und [Cu26Te12(PEt2Ph)12], die formal einen Cu3230+‐ bzw. Cu2624+‐Cluster enthalten. Rechnungen zur elektronischen Bandstruktur zeigen, dass eine Lokalisierung der formalen Oxidationszustände nicht möglich ist. Beide Verbindungen enthalten jeweils ein zentrales Cu6‐Oktaeder. Die kurzen Cu‐Cu‐Abstände können nicht mit einer d10‐d10‐Wechselwirkung interpretiert werden.

Professor Hansgeorg Schno È ckel zum 60. Geburtstag gewidmet.Inhaltsu È bersicht. Durch Umsetzungen von CuSCN mit AsPh(SiMe 3 ) 2 in Anwesenheit tertia È rer Phosphane ko È nnen die Verbindungen [Cu 4 (As 4 Ph 4 ) 2 (PRR' 2 ) 4 ] (1±3) (1: R = R' = n Pr, 2: R = R' = Et; 3: R = Me, R' = n Pr) und [Cu 14 (AsPh) 6 (SCN) 2 (PEt 2 Ph) 8 ] (4) dargestellt werden. Die Verwendung von CuCl anstelle von CuSCN fu È hrt zu den Clusterkomplexen [Cu 14 (AsPh) 6 Cl 2 (PRR' 2 ) 8 ] (5±6) (5: R = R' = Et; 6: R = Me, R' = n Pr), [Cu 12 (AsPh) 6 (PPh 3 ) 6 ] (7) und [Cu 10 (AsPh) 4 Cl 2 (PMe 3 ) 8 ] (8). Durch Reaktionen von CuOAc mit As(SiMe 3 ) 3 in Anwesenheit tertia È rer Phosphane erha È lt man die Verbindungen [Cu 12 (AsSiMe 3 ) 6 (PRR' 2 ) 6 ] (9±11) (9: R = R' = Et; 10: R = Ph, R' = Et; 11: R = Et, R' = Ph) und [Cu 8 (AsSiMe 3 ) 4 (P t Bu 3 ) 4 ] (12). Die Charakterisierung der Produkte erfolgte in allen Fa È llen durch Einkristall-Ro È ntgenstrukturanalyse. Als auffa È lligstes Strukturmerkmal haben 1±3 je zwei (As 4 Ph 4 ) 2± -Ketten als Liganden. 4±12 enthalten dagegen diskrete AsR 2± -Liganden (R = Ph, SiMe 3 ).Abstract. Through the reaction of CuSCN with AsPh-(SiMe 3 ) 2 in the presence of tertiary phosphines the compounds [Cu 4 (As 4 Ph 4 ) 2 (PRR' 2 ) 4 ] (1±3) (1: R = R' = n Pr, 2: R = R' = Et; 3: R = Me, R' = n Pr) and [Cu 14 (AsPh) 6 (SCN) 2 -(PEt 2 Ph) 8 ] (4) can be synthesised. Using CuCl instead of CuSCN results to the cluster complexes [Cu 14 (AsPh) 6 Cl 2 (PRR' 2 ) 8 ] (5±6) (5: R = R' = Et; 6: R = Me, R' = n Pr), [Cu 12 (AsPh) 6 (PPh 3 ) 6 ] (7) and [Cu 10 (AsPh) 4 Cl 2 -(PMe 3 ) 8 ] (8). Through reactions of CuOAc with As(SiMe 3 ) 3 in the presence of tertiary phosphines the compounds [Cu 12 (AsSiMe 3 ) 6 (PRR' 2 ) 6 ] (9±11) (9: R = R' = Et; 10: R = Ph, R' = Et; 11: R = Et, R' = Ph) and [Cu 8 (AsSiMe 3 ) 4 -(P t Bu 3 ) 4 ] (12) can be obtained. In each case the products were characterised by single-crystal-X-ray-structure-analyses. As the main structure element 1±3 each have two As 4 Ph 4 2±chains as ligands. In contrast 4±12 contain discrete AsR 2±ligands.