An Unpredictable Reaction of tBu2PHO·BCl3 in the Presence of Water

• Published in: Journal of chemical crystallography 2012-05, Vol.42 (5), p.472-474
• Main Authors: Sänger, Inge, Schödel, Frauke, Bolte, Michael, Lerner, Hans-Wolfram
• Format: Article
• Language: English
• Subjects: Chemistry; Chemistry and Materials Science; Crystallography and Scattering Methods; Inorganic Chemistry; Organometallic Chemistry; Original Paper; Physical Chemistry
• ISSN: 1074-1542; 1572-8854
• DOI: 10.1007/s10870-011-0271-8

When a benzene solution of t Bu 2 PHO·BCl 3 was exposed to air at room temperature, the phosphonium chloride [ t Bu 2 PH 2 ]Cl was formed together with di- tert -butylphosphinic acid, t Bu 2 PO(OH). X-ray quality crystals of the hydrochloride [ t Bu 2 PH 2 ]Cl·HCl were obtained from the reaction solution at room temperature. The hydrochloride [ t Bu 2 PH 2 ]Cl·HCl crystallizes in the monoclinic space group P 2 1 /m , a  = 6.3012(7) Å, b  = 6.8970(10) Å, c  = 14.5011(15) Å, β  = 99.376(9)°, V  = 621.79(13) Å 3 , Z  = 2, d calcd  = g cm −3 1.165; R 1 = 0.0510, wR 2 = 0.1503 for 1,129 reflections with I  > 2σ( I ). The crystal was a non-merohedral twin with a contribution of 0.353(7) of the minor component. The structure is composed of discrete di- t -butylphosphonium cations and Cl anions. Both are located on a crystallographic mirror plane and are connected by P–H···Cl hydrogen bonds. Graphical Abstract When a benzene solution of t Bu 2 PHO·BCl 3 was exposed to air at room temperature, the phosphonium chloride [ t Bu 2 PH 2 ]Cl was formed together with di- tert -butylphosphinic acid, t Bu 2 PO(OH). The crystal turned out to be a non-merohedral twin (twin law: 0.777 0−0.226/0 − 1 0/−1.765 0 − 0.775) with a fractional contribution of the minor twin component of 0.353(7).