title: Synthesis of heteroatomic bridged paracyclophanes.
abstract: Heteroatomic bridged paracyclophanes were obtained by two independent synthetic approaches. The required precursors consist of para R2SiCl (R = Me, iPr) substituted aromatic rings (2 and 4). They were subsequently functionalised by using NH3, [LiPH2(dme)] or LiAl(PH2)4. In the case of the Me-substituted species 2, the reaction with NH3directly yielded the Si2N bridged paracyclophane 5. The Si2P incorporated derivative 10 was obtained by lithiation of p-C6H4(SiiPr2PH2)2(9) and subsequent salt metathesis with the chlorosilane 4. The second approach involves the use of GaEt3in the formation of four membered (GaPn)2cycles (Pn = N, P). p-[C6H4{SiiPr2N(H)GaEt2}2]2(11) and p-[C6H4{SiiPr2P(H)GaEt2}2]2(12) represent the first examples of stable (GaPn)2cis isomers as the trans species did not appear in solution. Although 11 and 12 show a similar coordination pattern, they differ in the orientation of the aromatic systems: in the solid structure, 11 adopts a - for paracyclophanes so far unique - T-shape conformation of the phenyl rings, while 12 shows the predominant coplanar orientation. All cyclophanes were characterized by X-ray diffraction, elemental analysis, NMR and IR spectroscopy.
authors.affiliation: Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften (WZMW), Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043 Marburg, Germany. haenisch@chemie.uni-marburg.de.
authors.forename: K
authors.initials: K
authors.lastname: Reuter
authors.affiliation: Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften (WZMW), Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043 Marburg, Germany. haenisch@chemie.uni-marburg.de.
authors.forename: R G M
authors.initials: RG
authors.lastname: Maas
authors.affiliation: Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften (WZMW), Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043 Marburg, Germany. haenisch@chemie.uni-marburg.de.
authors.forename: A
authors.initials: A
authors.lastname: Reuter
authors.affiliation: Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften (WZMW), Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043 Marburg, Germany. haenisch@chemie.uni-marburg.de.
authors.forename: F
authors.initials: F
authors.lastname: Kilgenstein
authors.affiliation: Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften (WZMW), Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043 Marburg, Germany. haenisch@chemie.uni-marburg.de.
authors.forename: Y
authors.initials: Y
authors.lastname: Asfaha
authors.affiliation: Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften (WZMW), Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35043 Marburg, Germany. haenisch@chemie.uni-marburg.de.
authors.forename: C
authors.identifier: http://orcid.org/0000-0002-6298-8937
authors.initials: C
authors.lastname: von Hänisch