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Making and Breaking of P–P Bonds with Low‐Valent Transition‐Metal Complexes
Author(s) -
GómezRuiz Santiago,
Frank René,
Gallego Beatriz,
Zahn Stefan,
Kirchner Barbara,
HeyHawkins Evamarie
Publication year - 2011
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.201001137
Subject(s) - chemistry , covalent bond , transition metal , crystallography , ligand (biochemistry) , stoichiometry , crystal structure , metal , medicinal chemistry , stereochemistry , catalysis , organic chemistry , biochemistry , receptor
The 1:1 or 1:2 stoichiometric reaction of [Na 2 (thf) 4 (P 4 Mes 4 )] ( 1 ; Mes = 2,4,6‐Me 3 C 6 H 2 ) with [{RhCl(cod)} 2 ] (cod = 1,5‐cyclooctadiene) gave a mixture of compounds of which [Na(thf) 3 ][Rh(P 3 Mes 3 )(cod)] ( 2 ) with a trimesityltriphosphane‐1,3‐diide ligand was structurally characterized. Density functional calculations on 2 confirmed the structural parameters obtained by X‐ray diffraction studies. Shared electron number and natural bond orbital analyses indicated only weak interactions between Na and P, which were found to be even weaker than the Na–Rh interactions with covalent contribution. When an excess of 1 was used (3:1 or 4:1), 2 was also obtained as the major product together with small amounts of the side‐products cyclo ‐P 6 Mes 6 ( 3 ) and [Na 3 (Et 2 O)(P 4 Mes 4 )(PHMes)] ∞ ( 4 ). Compounds 3 and 4 were only characterized by single‐crystal X‐ray diffraction studies. Their formation indicates that the reaction includes the breaking and making of P–P bonds to give (P 3 Mes 3 ) 2– , PHMes – , and cyclo ‐P 6 Mes 6 , although the mechanism is unclear. Furthermore, the reaction of 1 with 2 equiv. of [AgCl(PPh 3 ) 2 ] gave the tetranuclear compound [Ag 4 (P 6 Mes 6 ) 2 ] ( 5 ) in which the novel (P 6 Mes 6 ) 2– ion also indicates degradation of the P 4 chain followed by P–P bond formation.