Hexacoordinate Phosphorus. 7. Synthesis and Characterization of Neutral Phosphorus(V) Compounds Containing Divalent Tridentate Diphenol Imine, Azo, and Thio Ligands
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- 作者：Chih Y. Wong ; Robert McDonald ; and Ronald G. Cavell
- 刊名：Inorganic Chemistry
- 出版年：1996
- 出版时间：January 17, 1996
- 年：1996
- 卷：35
- 期：2
- 页码：325 - 334
- 全文大小：561K
- 年卷期：v.35,no.2(January 17, 1996)
- ISSN：1520-510X
文摘
The reactions of bis(trimethylsilyl)ated forms of theSchiff base ligandsN-(2-hydroxyphenyl)salicylideneamine{(HO)C6H4N(CH)C6H4(OH)},N-(4-tert-butyl-2-hydroxyphenyl)salicylideneamine{(HO)(tBu)C6H3N(CH)C6H4(OH)}, N-(2-hydroxy-4-nitrophenyl)salicylideneamine{(HO)(O2N)C6H3N(CH)C6H4(OH)},and the structurallyrelated ligand 2,2'-azophenol with halogeno- and(trifluoromethyl)halogenophosphoranes yield a series ofneutralhexacoordinate phosphorus(V) compounds by means of trimethylsilylhalide elimination. In all of these casesthe ligands chelate in a meridional conformation in which bicyclicfive- and six-membered chelate rings areformed through structures containing two phenolic P-O bonds and oneN-P bond. The hexacoordinate natureof these compounds is evidenced by their high-field 31P NMRchemical shifts and their characteristic JPFcouplingpatterns and is further substantiated by the crystal structures of{O(tBu)C6H3N(CH)C6H4O}PCl3and{OC6H4N=NC6H4O}PF3.Crystal data for{O(tBu)C6H3N(CH)C6H4O}PCl3:triclinic, space group P
(No. 2),a = 11.167(1) Å, b = 15.684(1) Å,c = 17.047(2) Å, V = 2840(1)Å3, Z = 2. Final R andRw values were 0.051and 0.079, respectively. Crystal data for{OC6H4N=NC6H4O}PF3:monoclinic, space group P21/c (No.14), a= 6.9393(8) Å, b = 12.450(2) Å, c= 13.907(2) Å, V = 1190.7(6) Å3,Z = 4. Final R andRw values were 0.045and 0.056, respectively. The molecular structures of{O(tBu)C6H3N(CH)C6H4O}PCl3and{OC6H4N=NC6H4O}PF3 show that in both cases the Schiff base ligand chelatesoccupy the meridional plane about the six-coordinatephosphorus atom. In the case of{OC6H4N=NC6H4O}PF3the equivalent nitrogen atoms in the chelate rings aredisordered to form half-occupancy pairs. The silylated form of therelated thiobis(phenol),2,2'-thiobis(4,6-tert-butylphenol), reacted similarly with pentavalent halides to form thesix-coordinate complex [{2-O-3,5-(tBu)2C6H2}2S]PCl3which was also verified by a crystal structure. Crystal data for[{2-O-3,5-(tBu)2C6H2}2S]PCl3: monoclinic P21/n, a =13.989(2), b = 13.594(2), c =16.483(2) Å, 
= 97.98(2)
, V =3104(2) Å3, Z = 4; finalR and Rw values were 0.039and 0.052, respectively. In contrast to the above six coordinatecomplexes, thiscompound possesses a facial structure in which two phenoxy substituentsform planar chelates centered on thebridging sulfur and intersecting at the P-S axis. The P-S bondlength, 2.331(1) Å, is slightly shorter than hasbeen previously observed in the example wherein the ligand possessestwo tert-butyl groups and the phosphoruscarries three OCH2CF3 substituentsindicating stronger interaction between P and S in the presentcase.
(No. 2),a = 11.167(1) Å, b = 15.684(1) Å,c = 17.047(2) Å, V = 2840(1)Å3, Z = 2. Final R andRw values were 0.051and 0.079, respectively. Crystal data for{OC6H4N=NC6H4O}PF3:monoclinic, space group P21/c (No.14), a= 6.9393(8) Å, b = 12.450(2) Å, c= 13.907(2) Å, V = 1190.7(6) Å3,Z = 4. Final R andRw values were 0.045and 0.056, respectively. The molecular structures of{O(tBu)C6H3N(CH)C6H4O}PCl3and{OC6H4N=NC6H4O}PF3 show that in both cases the Schiff base ligand chelatesoccupy the meridional plane about the six-coordinatephosphorus atom. In the case of{OC6H4N=NC6H4O}PF3the equivalent nitrogen atoms in the chelate rings aredisordered to form half-occupancy pairs. The silylated form of therelated thiobis(phenol),2,2'-thiobis(4,6-tert-butylphenol), reacted similarly with pentavalent halides to form thesix-coordinate complex [{2-O-3,5-(tBu)2C6H2}2S]PCl3which was also verified by a crystal structure. Crystal data for[{2-O-3,5-(tBu)2C6H2}2S]PCl3: monoclinic P21/n, a =13.989(2), b = 13.594(2), c =16.483(2) Å, = 97.98(2), V =3104(2) Å3, Z = 4; finalR and Rw values were 0.039and 0.052, respectively. In contrast to the above six coordinatecomplexes, thiscompound possesses a facial structure in which two phenoxy substituentsform planar chelates centered on thebridging sulfur and intersecting at the P-S axis. The P-S bondlength, 2.331(1) Å, is slightly shorter than hasbeen previously observed in the example wherein the ligand possessestwo tert-butyl groups and the phosphoruscarries three OCH2CF3 substituentsindicating stronger interaction between P and S in the presentcase.