Synthesis and structure of two lithium terphenyls and a “halide rich” terphenyl lithium species

Ligand influences on homoleptic Group 12 m-terphenyl complexes

“…The reaction between the three lithium complexes [2,6-Ar 2 C 6 H 3 Li] 2 (Ar = 2,6-Xyl; 3,5-Xyl; Pmp) 16,17 and ZnCl 2 , CdCl 2 or HgBr 2 in a mixture of toluene and THF at room temperature yields the diaryl complexes [2,6-(2,6-Xyl) 2 C 6 The NMR spectroscopic measurements on 1-9 all indicate one ligand environment in solution. This is in contrast to the NMR spectra recorded for (2,6-Naph 2 C 6 H 3 ) 2 Zn and (2,6-Naph 2 C 6 H 3 ) 2 M(OEt 2 ) (M = Cd, Hg; Naph = 1-C 10 H 7 ), where syn and anti ligand conformations lead to multiple isomers of the complexes in solution.…”

“…Hexane, THF and toluene were pre-dried over Na wire prior to passing through a column of activated alumina (hexane) or distilled over Na/benzophenone (THF) or potassium (toluene), followed by storage over a potassium mirror (hexane, toluene) or 4 Å molecular sieves (THF). Lithium complexes [2,6-Ar 2 C 6 H 3 Li] 2 (Ar = 2,6-Xyl, 3,5-Xyl, Pmp) 16,17 and anhydrous ZnCl 2 and CdCl 2 were prepared by minor modifications of literature methods. 26 HgBr 2 was dried in vacuo at room temperature for 24 hours prior to use.…”

Synthesis and characterisation of complexes of the 2,6-diphenoxyphenyl ligand

“…Unlike these more symmetrical aryl bridged dimers, the Li (1) [3]. The central ligand aryl rings sit at an angle of 38.25 (11) out of the best mean plane of the Li(1)eC (1)eLi(1_2)eC(1_2) moiety; this is in the range of that reported for dimeric m-terphenyl lithium complexes (32.4e43.5 ) [21,24], but smaller than that for other pincer-type lithium dimers such as [2,6-(Me 2 PCH 2 ) 2 C 6 H 3 Li] 2 [14]. In Single crystals of 2 and 3 of quality suitable for X-ray diffraction were obtained by the storage of saturated hexane solutions at À30 C. The crystal structure of 2 is shown in Fig.…”

“…The (2) 1.418(2) C(2)eO(1)eC (7) 117.46(13) C(7)eO(1) 1.392(2) C(6)eO(2)eC (13) 120.35(14) C(13)eO (2) 1.378 (2) :C(7) ring and central phenyl ring 76.97(6) C(1)eC (2) 1.388 (2) :C(13) ring and central phenyl ring 64.43(5) C(1)eC (6) 1.393 (2) :C(7) and C (13) (11) Symmetry operation _2 ¼ Àx, Ày þ 1, Àz þ 1. ey þ 1, ez þ 1)], akin to related mterphenyl dimers [2,6-(2,6-Me 2 C 6 H 3 ) 2 C 6 H 3 Li] 2 and [2,6-(2,3,4,5,6-Me 5 C 6 ) 2 C 6 H 3 Li] 2 [21]. The distance between the lithium centres in [1.Et 2 O] 2 [Li(1)/Li(1_2) ¼ 2.585(6) Å] is similar to that found in dimeric complexes [2,4,6-(CF 3 ) 3 C 6 H 2 Li] 2 and [2,6-(Me 2 PCH 2 ) 2-C 6 H 3 Li] 2 [13,14].…”

Intramolekulare Reaktionen transienter Phosphenium‐ und Arsenium‐Ionen führen zur Bildung isolierbarer 9‐Phospha‐ und 9‐Arsena‐Fluorenium‐Ionen

“…Wir haben daher unsere Synthesestrategie angepasst und unsere Aufmerksamkeit auf ähnliche m ‐Terphenyl‐Substituenten gerichtet, in denen die flankierenden Arylgruppen permethyliert sind. Ausgehend von 2,6‐(Me 5 C 6 ) 2 C 6 H 3 Li und ECl 3 (E=P, As) haben wir nun die Bis‐ m ‐terphenylpniktogenfluoride (2,6‐{Me 5 C 6 } 2 C 6 H 3 ) 2 EF ( 1 a , E=P; 1 b , E=As) hergestellt. Die Synthese, Lösungs‐NMR‐ und Festkörperstruktur‐Merkmale von 1 a und 1 b ähneln denen der zuvor beschriebenen Verbindungen (2,6‐Mes 2 C 6 H 3 ) 2 EF (E=P, As).…”