Ru(ii) and Rh(iii) porphyrin complexes of primary phosphine-substituted porphyrinsDedicated to the memory of Bhaskar G. Maiya.

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.…”

Isolable Phosphaalkenes Bearing 2,4,6-Trimethoxyphenyl and 2,6-Bis(trifluoromethyl)phenyl as P-Substituents

“…Notably, this is among the highest field shifts reported for a primary phosphine (cf. Ph–CC–PH 2 : δ P = −176). , In the unlikely event that reduction was incomplete, additional LiAlH 4 was added to complete the reduction. After workup, the desired phosphine 3a was isolated as colorless crystals (yield = 40%).…”

Ruthenium(ii) and rhodium(iii) porphyrin phosphine complexes: influence of substitution pattern on structure and electronic properties

“…[16][17][18] We have exploited this coordination chemistry to create supramolecular multi-porphyrin arrays. [19][20][21] The bonding, however, is not kinetically inert, and the ligand exchange can be used to create dynamic combinatorial libraries. 22,23 Other examples of Ru-and Rh-porphyrin phosphine complexes in supramolecular assemblies are scarce, and normally nitrogen complexation is favoured for the creation of supramolecular assemblies with either ruthenium [24][25][26][27] or rhodium 28 porphyrins, in particular also making use of the reversible coordination to create dynamic switching systems.…”