Copper(I) Pseudohalide Coordination Polymers containing Macrocyclic Methylcycloarsoxane (CH₃AsO)_n (n = 4, 5) or 1, 7‐Dithia‐18‐crown‐6 Bridging Units. Kupfer(I)‐Pseudohalogenid‐haltige Koordinationspolymere mit den Makrozyklen Methylcycloarsoxan (CH₃AsO)_n (n = 4, 5) oder 1, 7‐Dithia‐18‐Krone‐6 als Brückenliganden

Abstract

Treatment of an acetonitrile solution of CuCN with methylcycloarsoxane (CH 3 AsO) n at 110°C affords the coordination polymer 3 ϱ [CuCN{cyclo-(CH 3 AsO) 4 }] (1), in which infinite CuCN zigzag chains are linked by µ-As 1 ,As 3 cyclotetramers (CH 3 AsO) 4 into an open 3-D framework. Under similar solvothermal conditions, reaction of CuSCN with (CH 3 AsO) n in the presence of KSCN leads to metal-mediated ring expansion of the cycloarsoxane to yield the complex 1 ϱ [{K[cyclo-(CH 3 AsO) 5 ] 2 }Cu(NCS) 2 ] (2). This contains discrete [Cu(NCS-κN) 2 {cyclo-(CH 3 AsO) 5 κAs} 2 ] Ϫ anions that bridge κ 10 O coordinated potassium 709 cations into infinite chains. In contrast, the structure directing role of the [K(1,7DT18C6) 2 ] ϩ sandwich building units for the solvothermal product 3 ϱ [{K(1,7DT18C6) 2 }Cu 6 (CN) 7 ] (3) (1,7DT18C6 ϭ 1,7dithia-18-crown-6) leads to formation of an open 3 ϱ [{Cu 6 (CN) 7 } Ϫ ] framework. Individual [K(1,7DT18C6) 2 ] ϩ moieties bridge Cu Atoms in a µ-S 1 ,S 7 mode and are encapsulated within the large [Cu 26 (CN) 28 ] 2Ϫ cages of the cyanocuprate(I) network.

Silicon Analogues of Crown Ethers and Cryptands: A New Chapter in Host–Guest Chemistry?

“…Although the weaker basicity of cyclosiloxanes compared to that of organic polyethers will likely restrict the range of metal‐ion complexes of D n , the observation of metal‐templated ring transformations may be of considerable significance 16. 25 For instance, the series of polysilathianes (R 2 SiS) n is limited to dimeric ( n =2) and trimeric ( n =3) ring systems even for small substituents (R=Me) 26. Templation of these S‐donor ligands (or their Se analogues)27 by soft metal cations may promote ring transformations to give larger SiE (E=S, Se) rings.…”

Siliciumanaloga von Kronenethern und Cryptanden: ein neues Kapitel in der Wirt‐Gast‐Chemie?

“…Obwohl die geringere Basizität von Cyclosiloxanen (verglichen mit organischen Polyethern) voraussichtlich den Bereich von Metallkomplexen mit D n ‐Liganden beschränken wird, ist die Beobachtung von Ringtransformationen an einem Metalltemplat von erheblicher Bedeutung 16. 25 So ist die Serie der Polysilathiane (R 2 SiS) n selbst für kleine Substituenten (R=Me) auf dimere ( n =2) und trimere Ringe ( n =3) beschränkt 26. Die Koordination dieser Schwefeldonorliganden (oder ihrer Selenanaloga)27 durch weiche Metallkationen könnte Ringtransformationen fördern und zu größeren Si‐E‐Ringen führen (E=S, Se).…”