Triphenylphosphine oxide complexes

Figure 5 Partial structural details for hexalds(benzotriazolyl)hexakis(allylamine)trisnickel(II) triphenylphosphine oxide complex (19 Ni[(BT)jNi(AA)j]2 2PI13PO) (76AX(B)7I4)...

Ligand exchange reactions of triphenylphosphine oxide complexes of yttrium compounds were studied. ... 

The triphenylphosphine oxide complexes (13.24a,b) have relatively simple structures. In the case of the fluoride, however, the hydrogen atom is located closer to F than to O and it may be argued that proton transfer has not taken place. In crystalline PhjPO HNO3 (13.24c) the proton remains closer to the nitrate group while in PhjAsO HNO3 it appears to lie closer to the 0=As unit (13.24d). 

The use of a catalyst such as cadmium oxide increases the yield of dibasic acids to about 51% of theoretical. The composition of the mixed acids is about 75% C-11 and 25% C-12 dibasic acids (73). Reaction of undecylenic acid with carbon monoxide using a triphenylphosphine—rhodium complex as catalyst gives 11-formylundecanoic acid, which, upon reaction with oxygen in the presence of Co(II) salts, gives 1,12-dodecanedioic acid in 70% yield (74). 

Samarium, tris(triphenylphosphine oxide)bis-(diethyldithiophosphato)-structure, 1,78 Samarium complexes dipositive oxidation state hydrated ions, 3, 1109 Samarium(III) complexes salicylic acid crystal structure, 2, 481 Sampsonite, 3, 265... 

With cobalt(ii) chloride, complexes of the monophosphazene, PhgP=NH (= L), of stoicheiometry CoCl2L,THF and C0CI2L2 have been isolated. Their i.r. and u.v. spectra were compared with analogous complexes of triphenylphosphine oxide. 

The force constants of the Ni—P bond in P " nickel carbonyl complexes increase in the order MeaP < PHg < P(OMe)a < PFs. This order is different from that of the donor-acceptor character, as estimated from uco-The lengthening of the P—O bond of triphenylphosphine oxide upon complexation with uranium oxide has been estimated by i.r. spectroscopy. However, A -ray diffraction shows little difference in the P-O bond lengths (see Section 7). Some SCF-MO calculations on the donor-acceptor properties of McaPO and H3PO have been reported. 

The crystal structures of a number of diphosphine disulphides (121) and (122) show a remarkable constancy in the bond lengths. Two types of molecule are observed in the crystal of the tetramethyl compound (121, X = Y = Me). The crystal structure of triphenylphosphine oxide (P—C 176 pm, P—O 164 pm) varies little from that observed in the uranium oxide complexes, and does not confirm P—O bond lengthening in complexes, as indicated by vp=.o (see Section 3C). 

Remarkable complex ions are formed in reactions of triphenylphosphine oxide withPOClg (62) ... 

The majority of gold(I) carbene complexes are pure organometallic compounds and the are out of the scope of this work. Some halide or triphenylphosphine carbene complexes are known and they will be considered here. Nucleophilic addition of alcohols or amines to gold-coordinated isocyanides is one of the best-established methods to obtain gold carbene derivatives. The reaction of H[Au(CN)2] with propene oxide and estirene oxide yields (cyano)carbene complexes (380) avoiding the intermediate step.2257 A cyclic carbene compound is obtained by reaction of a dinuclear isocyanide with amine (Scheme 32).2258... 

ErQ3 gives both PL and EL emission at 1,500 nm.207-209 Red light (614 nm) is emitted by [Eu(TTFA)3(phen)] (Figure 2(a)) doped in a poly(A-vinylcarbazole) layer.210 The complex [Eu(TTFA)3(TPPO)2] (TPPO = triphenylphosphine oxide, see Figure 2(f)) emits in the red when incorporated in OLEDs,211,212 behavior which is enhanced when the material is heat treated.204 Near-IR EL and PL emission was observed from blends of polyfp-phenylene-vinylene) with [Yb(TPP)(ACAC)] and [Er(TPP)(ACAC)] (H2TPP is 5,10,15,20-tetraphenylporphyrin) by both EL and PL 213... 

A 1 1 complex of a 4-aryltriazole with triphenylphosphine oxide is also reported. ... 

Scheme 12.7 Effect of thermal pretreatment of the support on the nature of the immobilized silylamide surface complex and determination of the bonding strength of siloxane bridges by displacement with triphenylphosphine oxide on an AS-3 0 m hybrid material.

The chromium tricarbonyl complex 429 of triphenylphosphine oxide is hthiated and silylated (in situ quench) by 360 and McsSiCl to give 430 (X = Si) in 90% yield and 73% ee (Scheme 175) °. Interestingly, the sense of asymmetric induction is reversed from the anisole result. With two equivalents of chiral base, bis-sUyl compounds 432 could be formed. 

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