New organotin(IV)-phosphoramidate complexes: Breaking of the PO鈰疕N hydrogen bonds and its influence on the molecular packing

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• 作者：Alejandro J. Metta-Magañ ; a^a ; Mehrdad Pourayoubi^b ; ^{mehrdad_pourayoubi@yahoo.com} ; Keith H. Pannell^a ; ¹ ; ^{kpannell@utep.edu} ; Mahnaz Rostami Chaijan^b ; Hossein Eshtiagh-Hosseini^b
• 关键词：Organotin(IV) ; Tris(alkylamido)orthophosphate ; Phosphoric triamide ; NMR experiment ; X-ray crystallography
• 刊名：Journal of Molecular Structure
• 出版年：2012
• 期刊代码：62_00222860
• 类别：ch
• 出版时间：25 April, 2012
• 卷：1014
• 期：Complete
• 页码：38-46
• 文件大小：1380 K

摘要

Phosphoryl donor (PO) ligands (^tBuNH)₃PO (1), (C₆H₅CH₂NH)₃PO (2) and (4-NO₂-C₆H₄C(O)NH)(OC₄H₈N)₂PO (3) were used for the preparation of new organotin(IV) complexes Cl₂Me₂Sn(PO)₂ (4-6). The environment at the nitrogen atom in the phosphoramide ligand is almost planar and it does not take part in hydrogen bonding as an acceptor in complexes 4-6, reflecting its low Lewis base character, and the Sn atom is located at the inversion center, making half of the molecule related by symmetry. The Sn coordination geometry is octahedral with the pair of similar ligands in a trans orientation. The crystal structure of 6 demonstrates that the phosphoryl group, and not the carbonyl group, coordinates to the tin center. A blue shift in the NH stretching frequencies of 4 and 6, in comparison to the free ligands 1 and 3, is attributed to vanish of the NH鈰疧 hydrogen bonds, but the PO stretching frequencies of the complexes exhibit no significant changes with respect to the related ligands because of minor differences caused by forming the PO鈰疭n instead of the PO鈰疕N. The NMR experiments indicate an increasing in ²J(P,H) coupling constants in 4 and 6 and ³J(P,C) in 5 compared to the related ligands. The hydrogen bond pattern of the ligands and the complexes were compared.