One-Pot Synthesis of Metal Primary Phosphine Complexes from OPCl₂R or PCl₂R. Isolation and Characterization of Primary Alkylphosphine Complexes of a Metalloporphyrin

Orthogonal Coordination Chemistry of PTA toward Ru(II) and Zn(II) (PTA = 1,3,5-Triaza-7-phosphaadamantane) for the Construction of 1D and 2D Metal-Mediated Porphyrin Networks

“…Even though the chemical shifts of the phenyl signals are not particularly affected, by virtue of the increased symmetry the o H resonancethat was split into two well-resolved doublets in the spectrum of [Ru­(TPP)­(CO)]is a sharp doublet in that of [Ru­(TPP)­(PTA-κ P ) 2 ] (Figure and Figure S1). Consistent with what found with similar [Ru­(por)­(P) 2 ] adducts, ,− the Soret band in the electronic absorption spectrum of 1 is considerably red-shifted compared to [Ru­(TPP)­(CO)] (431 vs 408 nm).…”

“…It is well-known from the literature that whereas pyridine or azole ligands (N) replace the labile solvent molecule trans to CO in [Ru­(por)­(CO)­(S)] compounds (e.g., por = TPP; S = MeOH or EtOH, typically not indicated in the formula), affording derivatives of the general formula [Ru­(por)­(CO)­(N)], − most phosphine and phosphite ligands (P) under mild conditions replace easily also the carbonyl ligand yielding disubstituted compounds of formula [Ru­(por)­(P) 2 ]. ,− Monosubstituted [Ru­(por)­(CO)­(P)] intermediates with tertiary phosphines have been occasionally isolated, whereas in most other cases, due to the weakening of the carbonyl ligand by the phosphine trans effect, they could not be isolated but were characterized spectroscopically in solution . To our knowledge, with the exception of a private communication from Sanders and co-workers, no X-ray structure of such an intermediate has been reported yet.…”

Primary and Secondary Phosphine Complexes of Iron Porphyrins and Ruthenium Phthalocyanine: Synthesis, Structure, and P−H Bond Functionalization

“…In contrast, the ruthenium(II) phthalocyanines 3 and 4 all exhibit a remarkable stability toward air in both the solid state and solution . The stability of [Ru II (Pc)(PH 2 Ph) 2 ] ( 3a ) and [Ru II (Pc)(PHPh 2 ) 2 ] ( 4 ) is comparable to that of [Ru II (F 20 -TPP)(PH 2 Ph) 2 ] and [Ru II (F 20 -TPP)(PHPh 2 ) 2 ]; the latter complexes bear a fluorinated porphyrin ligand and were found to exhibit the highest stability among all previously reported PH 2 R complexes of ruthenium porphyrins …”

“…At room temperature, the 1 H and 31 P NMR spectra of [Fe II (F 20 -TPP)(PH 2 R) 2 ] ( 1a , b ) in CDCl 3 solution show broad signals, unlike those of their ruthenium analogues . The 1 H NMR spectrum of 1a is depicted in Figure as an example.…”

“…These primary alkynyl or alkenyl phosphine complexes are unstable in solution and have not been isolated . We have recently prepared a number of ruthenium porphyrin complexes of PH 2 R (R = aryl or alkyl) and PHPh 2 ; most of these complexes can be isolated in pure form.…”