Dppm related complexes

A new, versatile, one-step route to bis(diphenylphosphino)methane (dppm) metal carbonyl complexes involving NaBH4 reduction of a metal salt/dppm mixture under CO has been developed. The reaction outcome is determined by careful control of the conditions. With Co the complexes [Co(Ti -dppm)2(CO)][Co(CO)4], Co2( i-dppm)2(CO)4, Co2(g-dppm)2(g-CO)2(CO)2, and Co2(g-dppm)2(g-H)(g-PPh9)(CO)2 can dl be obtained as the major product. CoBH2(ti-dppm)(Ti -dppm)(CO)2, the first stable metallaborane, is a minor product and other and Ti -dppm-Co-CO complexes can also be prepared. With Ni, Ni( r -dppm)2(CO)2, Ni2(g-dppm)2(g-CO)(CO)2 and [Ni2(g-dppm)2( i-PPh2)(CO)2]X can all be prepared as major products. The heterobinuclear CoRh(g-dppm)2(CO)3 is similarly prepared from Co /Rh °/dppm/BH47CO reactions and related (e.g., Co-Mn, Ni-Cu) complexes can be prepared by two-step processes. Pd gives at least five Pd-dppm-CO complexes. 

The structures and emission properties of a series of related complexes [Pt(N C) (dppm)]+ (HN C = Hppy, Hmppy, Hpq) and [Pt(bph) (dppm)] have been investigated. The electronic absorption spectra of the complexes showed high-energy IL jt and low-energy MLCT... 

A new elongated dihydrogen complex of iridium, [Cp Ir(dmpm)H2] , has been synthesized by Pons and Heinekey ° and characterized by the use of NMR data which also included Vhp couplings. It has been established that the compound exists in the form of cis and trans arranged dihydride isomers Vhp = 6 Hz for the trans and Vhp = 20 Hz for the cis isomer have been found. The obtained data are in agreement with those reported earlier for the related [CpOs(dppm)H2] complex. ... 

The gold(l) complex [Au2(dppm)2] emits long-lived yellow phosphorescence as reported independently by Tackier and Che [110-112]. Emission is assigned to a do - po excited state centered on gold. Metal atoms are bonded in the excited state. Many related complexes have been characterized. Absorption spectra show intense transitions assigned as AUj do - -pa weaker spin-forbidden transitions can appear at longer wavelengths. 

S=G(NH2)2 Gp(dppf)][PF6] and [Ru Hrelated complexes [Ru / )-S=GG2H4S2 Gp(dppf)]Gr and [Ru / (A)-S=GG2H2S2 Gp(dppf)]Gr have been prepared directly from [RuGlGp(dppf)] and ethylene or vinylene trithiocarbonate, respectively, the presence of a chloride abstractor not being required in this case. " ... 

The A-frame complex [PtH2( -H)(M-dppm)2]+ reacts with CO to give [Pt2(CO)(H)C -dppm)2]+, which is transformed back to the original trihydrocomplex on reaction with H2. A related complex, [Pt2Me2(iM-H)(/M-dppm)2]+,... 

Pt Pt bond to give A-frame complexes.108 The related mixed-metal complex [PtCl(p-dppm)2Pd(C6F5)] also reacts with R2N+, S02, and alkynes to give A-frame complexes. 

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