An Acyclic Dimer of Cyclodiphosphazane {tBuHN(tBuNP)2OCH2}2 Containing Alkoxo and Amido Functionalities: Synthesis, Derivatization, Bi- (PdII, RhI), and Tetranuclear (PdII, AuI, RhIAuI) Transition Metal Complexes

被引:35
作者
Balakrishna, Maravanji S. [1 ]
Venkateswaran, Rarnalingam [1 ]
Mague, Joel T. [2 ]
机构
[1] Indian Inst Technol, Dept Chem, Phosphorus Lab, Bombay 400076, Maharashtra, India
[2] Tulane Univ, New Orleans, LA 70118 USA
关键词
STRUCTURAL-CHARACTERIZATION; COPPER(I) COORDINATION; REVERSIBLE CONVERSION; CHEMISTRY; MACROCYCLES; INSERTION; CRYSTAL; LIGANDS; PT(II); BONDS;
D O I
10.1021/ic801256h
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Acyclic bis(cyclodiphosphazane) [(BuHN)-Bu-t((BuNP)-Bu-t)(2)OCH2](2) (2) containing alkoxo and amido functionalities was synthesized by reacting cis-[(BuHN)-Bu-t((BuNP)-Bu-t)(2)Cl] (1) with ethylene glycol and upon further treatment with 4 equiv of elemental sulfur or selenium affords the corresponding tetrachalcogenides [(BuHN)-Bu-t((BuNPE)-Bu-t)(2)OCH2](2) (3, E = S; 4, E = Se) in quantitative yield. The reaction of 2 with 2 equiv of elemental sulfur results in the oxidation of only the amido-phosphorus atoms to form the di(sulfide) derivative [(BuHN)-Bu-t(S)P(mu-(BuN)-Bu-t)POCH2](2) (5). The reaction of 2 with 2 equiv of [PdCl(eta(3)-C3H5)](2) afforded the tetrametallic complex [{Pd(eta(3)-allyl)Cl)(4)((BuHN)-Bu-t((BuNP)-Bu-t)(2)OCH2}(2)] (7) containing four independent [PdCl2(eta(3)-C3H5)] moieties each coordinated to a phosphorus atom. In contrast, the reaction between [Pd(PEt3)Cl-2](2) and 2 leads to the addition of two metal atoms with the formation of [{Pd(PEt3)Cl}(2)-{(BuHN)-Bu-t((BuNP)-Bu-t)(2)OCH2}(2)] (8), in which alternating phosphorus atoms of the bis(cyclodiphosphazane) are coordinated to palladium. Interestingly, the palladium(II) atom coordinated to the phosphorus atom bearing the t-butylamino substituent adopts a trans geometry, whereas that coordinated to the phosphorus atom connected to the -OCH2CH2O- linker prefers a cis conformation. The reaction between 2 and [Rh(COD)Cl]2 produces exclusively the bimetallic complex [{Rh(COD)Cl}(2){(BuHN)-Bu-t((BuNP)-Bu-t)(2)OCH2}(2)] (6) irrespective of the stoichiometry of the reactants and the reaction conditions. In complex 6, only the alkoxo-phosphorus atoms are coordinated. However, complex 6 upon treatment with AuCl(SMe2) in a 1:2 ratio gives the heterometallic tetrasubstituted complex [{Rh(COD)Cl}(2)(AuCl)(2){(BuHN)-Bu-t((BuNP)-Bu-t)(2)OCH2}(2)] (10). The reaction between 4 equiv of AuCl(SMe2) and 2 resulted in the formation of a tetrametallic gold complex [(AuCl)(4){(BuHN)-Bu-t((BuNP)-Bu-t)(2)OCH2}(2)] (9). The crystal structures of 2-4 and 7-10 are reported.
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页码:1398 / 1406
页数:9
相关论文
共 46 条
[1]  
[Anonymous], 1997, S HELXS 97 SHELXL 97
[2]  
[Anonymous], 2000, SHELXTL VERS 6 10
[3]  
[Anonymous], 2006, APEX2 VERS 2 1 0
[4]  
Armarego W.L. F., 1996, PURIFICATION LAB CHE, V4th
[5]   Bis(imino)cyclodiphosph(V)azane complexes of late transition metals:: Efficient catalyst precursors for ethene and propene oligomerization and dimerization [J].
Axenov, KV ;
Leskelä, M ;
Repo, T .
JOURNAL OF CATALYSIS, 2006, 238 (01) :196-205
[6]   Bis(amido)cyclodiphosph(III)azane hafnium complexes and their activation by tris(perfluorophenyl)borane [J].
Axenov, KV ;
Klinga, M ;
Leskelä, M ;
Repo, T .
ORGANOMETALLICS, 2005, 24 (06) :1336-1343
[7]  
BAENZIGER NC, 1976, ACTA CRYSTALLOGR B, V32, P2547
[8]   Synthesis and molecular structure of 1,3-di-tert-butyl-2,4-bis(cyclodipentadienyl)iron(II) 1,3,2,4-diazadiphosphetidine, [Fe(η5-C5H4)2(PNtBu)2] [J].
Balakrishna, Maravanji S. ;
Mague, Joel T. .
ORGANOMETALLICS, 2007, 26 (18) :4677-4679
[9]   Chemistry of pnictogen(III)-nitrogen ring systems [J].
Balakrishna, Maravanji S. ;
Eisler, Dana J. ;
Chivers, Tristram .
CHEMICAL SOCIETY REVIEWS, 2007, 36 (04) :650-664
[10]   COORDINATION CHEMISTRY OF DIPHOSPHINOAMINE AND CYCLODIPHOSPHAZANE LIGANDS [J].
BALAKRISHNA, MS ;
REDDY, VS ;
KRISHNAMURTHY, SS ;
NIXON, JF ;
STLAURENT, JCTRB .
COORDINATION CHEMISTRY REVIEWS, 1994, 129 (1-2) :1-90