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Sherlock DJ, Chandrasekaran A, Prakasha TK, et al. Conformational Preference and Donor Atom Interaction Leading to Hexacoordination vs Pentacoordination in Bicyclic Tetraoxyphosphoranes(1). Inorg Chem. 1998;37(1):93-101doi: 10.1021/ic9704391.
Sherlock, D. J., Chandrasekaran, A., Prakasha, T. K., Day, R. O., & Holmes, R. R. (1998). Conformational Preference and Donor Atom Interaction Leading to Hexacoordination vs Pentacoordination in Bicyclic Tetraoxyphosphoranes(1). Inorganic chemistry, 37(1), 93-101. https://doi.org/10.1021/ic9704391
Sherlock, David J., et al. "Conformational Preference and Donor Atom Interaction Leading to Hexacoordination vs Pentacoordination in Bicyclic Tetraoxyphosphoranes(1)." Inorganic chemistry vol. 37,1 (1998): 93-101. doi: https://doi.org/10.1021/ic9704391
Sherlock DJ, Chandrasekaran A, Prakasha TK, Day RO, Holmes RR. Conformational Preference and Donor Atom Interaction Leading to Hexacoordination vs Pentacoordination in Bicyclic Tetraoxyphosphoranes(1). Inorg Chem. 1998 Jan 12;37(1):93-101. doi: 10.1021/ic9704391. PMID: 11670266.
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Inorg Chem. 1998 Jan 12;37(1):93-101. doi: 10.1021/ic9704391.

Conformational Preference and Donor Atom Interaction Leading to Hexacoordination vs Pentacoordination in Bicyclic Tetraoxyphosphoranes(1).

Inorganic chemistry

David J. Sherlock, A. Chandrasekaran, T. K. Prakasha, Roberta O. Day, Robert R. Holmes

Affiliations

  1. Department of Chemistry, Lederle Graduate Research Tower 701, Box 34510, University of Massachusetts, Amherst, Massachusetts 01003-4510.

PMID: 11670266 DOI: 10.1021/ic9704391

Abstract

New bicyclic tetraoxyphosphoranes all containing a six-membered oxaphosphorinane ring, C(6)H(8)(CH(2)O)(2)P(OC(12)H(8))(OXyl) (1), (C(6)H(4)O)(2)P(OC(12)H(8))(OXyl) (2), CH(2)[(t-Bu)(2)C(6)H(2)O](2)P(OC(12)H(8))(OXyl) (3), O(2)S[(t-Bu)MeC(6)H(2)O](2)P(OC(12)H(8))(OXyl) (4), and S[(t-Bu)MeC(6)H(2)O](2)P(OC(12)H(8))(OXyl) (5), were synthesized by the oxidative addition reaction of the cyclic phosphine P(OC(12)H(8))(OXyl) (6) with an appropriate diol in the presence of N-chlorodiisopropylamine. X-ray analysis revealed trigonal bipyramidal (TBP) geometries for 1-4 where the dioxa ring varied in size from six- to eight-membered. With a sulfur donor atom as part of an eight-membered ring in place of a potential oxygen donor atom of a sulfone group as in 4, the X-ray study of 5 showed the formation of a hexacoordinated structure via a P-S interaction. Ring constraints are evaluated to give an order of conformational flexibility associated with the (TBP) tetraoxyphosphoranes 4 > 3 approximately 1 > 2 which parallels the degree of shielding from (31)P NMR chemical shifts: 4 > 3 > 1 > 2. The six- and seven-membered dioxa rings in 1 and 2, respectively, are positioned at axial-equatorial sites, whereas the eight-membered dioxa ring in 3 and 4 occupies diequatorial sites of a TBP. V-T (1)H NMR data give barriers to xylyl group rotation about the C-OXyl bond. The geometry of 5 is located along a coordinate from square pyramidal toward octahedral to the extent of 60.7%. Achieving hexacoordination in bicyclic tetraoxyphosphoranes of reduced electrophilicity relative to bicyclic pentaoxyphosphoranes appears to be dependent on the presence of a sufficiently strong donor atom.

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