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Heptacoordinate Structures of Organotin Halides with Three Phosphine Donors: Halogen‐Substituent Effect on Geometry
Author(s) -
Kameo Hajime,
Kawamoto Tatsuya,
Sakaki Shigeyoshi,
Bourissou Didier,
Nakazawa Hiroshi
Publication year - 2019
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201900524
Subject(s) - chemistry , halogen , phosphine , substituent , tetrahedral molecular geometry , intramolecular force , electronegativity , coordination geometry , crystallography , molecular geometry , halogen bond , geometry , halide , density functional theory , stereochemistry , molecule , computational chemistry , crystal structure , alkyl , inorganic chemistry , hydrogen bond , organic chemistry , catalysis , mathematics
Structural studies were performed on heptacoordinate compounds of triorganotin halides {( o ‐Ph 2 P)C 6 H 4 } 3 SnX [X = F ( 1 ), Cl ( 3 ), Br ( 4 ), I ( 5 )] with three phosphine donors. The fluorostannane ( 1 ) has an unusual heptacoordinate geometry, in which the three phosphine donors interact with the Sn center around the opposite coordination site of the Sn–F bond ( a form). In contrast, the chloro ( 3 ) and bromo ( 4 ) analogues have highly distorted pentagonal‐bipyramidal geometries ( b form), while the iodo analogue ( 5 ) has a tricapped tetrahedral geometry ( c form). Although both b and c forms have two phosphine donors coordinating to the Sn center around the opposite site of the C ipso atoms and one phosphine donor coordinating to the Sn atom trans to the halogen atom, the geometry around the Sn center is much more distorted from tetrahedral geometry in b form than in c form. Density functional theory (DFT) calculations indicate that the presence of the halogen atom on the Sn center facilitates access from the opposite side of the halogen due to the strong electrostatic and intramolecular donor–acceptor transfer interactions. The difference in electronegativity of the halogen atoms also appear to contribute to structural modification by altering the halogen substituent, because a strongly electronegative halogen facilitates the formation of a structure that is highly distorted from the tetrahedral geometry (Bent's rule).