Wide-bite-angle diphosphinines: design, synthesis, and coordination properties

C. Müller; Z. Freixa; M. Lutz; A.L. Spek; D. Vogt; P.W.N.M. Leeuwen, van

doi:10.1021/om7003546

Wide-bite-angle diphosphinines: design, synthesis, and coordination properties

C. Müller, Z. Freixa, M. Lutz, A.L. Spek, D. Vogt, P.W.N.M. Leeuwen, van

Catalysis and Organometallic Chemistry

Research output: Contribution to journal › Article › Academic › peer-review

37 Citations (Scopus)

Abstract

A wide-bite-angle diphosphorin ligand I (Q = P) was designed and prepd., which exhibits structural features for a preferred formation of trans complexes. Acetylation of 1,1':2',1''-terphenyl by AcCl/AlCl3 gave 4,4''-diacetyl-1,1':2',1''-terphenyl, which upon condensation with 1,3-diphenyl-2-propen-1-one and HBF4Et2O gave bis-pyrylium salt I2BF4 (3, Q = O+). Reaction of 3 with P(SiMe3)3 gave the bis-phosphorin I (4, Q = P). Due to the linear orientation of the lone-pair electrons of the phosphorus donors in combination with an appropriate P-P distance, trans coordination toward a Rh center was obsd. and the corresponding [LRh(CO)I] (L = 4) complex could be characterized crystallog. Although typical reactivities usually obsd. for trans complexes were found, reaction of the diphosphorin 4 with the cis-enforcing precursor [Rh(nbd)2]BF4 did result in the formation of several species at low temp., to which cis-structures were attributed.

Original language	English
Pages (from-to)	834-838
Journal	Organometallics
Volume	27
Issue number	5
DOIs	https://doi.org/10.1021/om7003546
Publication status	Published - 2008

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Müller, C., Freixa, Z., Lutz, M., Spek, A. L., Vogt, D., & Leeuwen, van, P. W. N. M. (2008). Wide-bite-angle diphosphinines: design, synthesis, and coordination properties. Organometallics, 27(5), 834-838. https://doi.org/10.1021/om7003546

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abstract = "A wide-bite-angle diphosphorin ligand I (Q = P) was designed and prepd., which exhibits structural features for a preferred formation of trans complexes. Acetylation of 1,1':2',1''-terphenyl by AcCl/AlCl3 gave 4,4''-diacetyl-1,1':2',1''-terphenyl, which upon condensation with 1,3-diphenyl-2-propen-1-one and HBF4Et2O gave bis-pyrylium salt I2BF4 (3, Q = O+). Reaction of 3 with P(SiMe3)3 gave the bis-phosphorin I (4, Q = P). Due to the linear orientation of the lone-pair electrons of the phosphorus donors in combination with an appropriate P-P distance, trans coordination toward a Rh center was obsd. and the corresponding [LRh(CO)I] (L = 4) complex could be characterized crystallog. Although typical reactivities usually obsd. for trans complexes were found, reaction of the diphosphorin 4 with the cis-enforcing precursor [Rh(nbd)2]BF4 did result in the formation of several species at low temp., to which cis-structures were attributed.",

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AU - Müller, C.

AU - Freixa, Z.

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AU - Vogt, D.

AU - Leeuwen, van, P.W.N.M.

PY - 2008

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N2 - A wide-bite-angle diphosphorin ligand I (Q = P) was designed and prepd., which exhibits structural features for a preferred formation of trans complexes. Acetylation of 1,1':2',1''-terphenyl by AcCl/AlCl3 gave 4,4''-diacetyl-1,1':2',1''-terphenyl, which upon condensation with 1,3-diphenyl-2-propen-1-one and HBF4Et2O gave bis-pyrylium salt I2BF4 (3, Q = O+). Reaction of 3 with P(SiMe3)3 gave the bis-phosphorin I (4, Q = P). Due to the linear orientation of the lone-pair electrons of the phosphorus donors in combination with an appropriate P-P distance, trans coordination toward a Rh center was obsd. and the corresponding [LRh(CO)I] (L = 4) complex could be characterized crystallog. Although typical reactivities usually obsd. for trans complexes were found, reaction of the diphosphorin 4 with the cis-enforcing precursor [Rh(nbd)2]BF4 did result in the formation of several species at low temp., to which cis-structures were attributed.

AB - A wide-bite-angle diphosphorin ligand I (Q = P) was designed and prepd., which exhibits structural features for a preferred formation of trans complexes. Acetylation of 1,1':2',1''-terphenyl by AcCl/AlCl3 gave 4,4''-diacetyl-1,1':2',1''-terphenyl, which upon condensation with 1,3-diphenyl-2-propen-1-one and HBF4Et2O gave bis-pyrylium salt I2BF4 (3, Q = O+). Reaction of 3 with P(SiMe3)3 gave the bis-phosphorin I (4, Q = P). Due to the linear orientation of the lone-pair electrons of the phosphorus donors in combination with an appropriate P-P distance, trans coordination toward a Rh center was obsd. and the corresponding [LRh(CO)I] (L = 4) complex could be characterized crystallog. Although typical reactivities usually obsd. for trans complexes were found, reaction of the diphosphorin 4 with the cis-enforcing precursor [Rh(nbd)2]BF4 did result in the formation of several species at low temp., to which cis-structures were attributed.

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