Tri(3‐pyridyl)‐ and Tri(4‐pyridyl)­phosphine Chalcogenides and Their Complexes with ZnTPP (TPP = Tetraphenylporphyrinate). Issue 10 (9th March 2016)

• Record Type: Journal Article
• Authors: Dubován, Lea; Pöllnitz, Alpár; Silvestru, Cristian
• Is Part Of: European journal of inorganic chemistry. Issue 10(2016)
• Page Start: 1521
• Page End: 1527
• Publication Date: 2016-03-09
• Subjects: Phosphane ligands -- Chalcogens -- Heterometallic complexes -- Metal–organic frameworks -- Coordination modes; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201501333
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: The preparation, spectroscopic characterization (NMR and IR spectroscopy), and solid‐state structures of tri(3‐pyridyl)‐ and tri(4‐pyridyl)phosphine chalcogenides (E = O, S, Se) as well as their ability to behave as ligands for ZnTPP (TPP = tetraphenylporphyrinate) moieties are reported. In the solid state, the compounds from this family are three‐bladed molecular propellers that crystallize as racemates. Both triorganophosphine sulfides and selenides, (3‐Py)3 PE [Py = pyridyl, NC5 H4 ; E = S (2 ), Se (3 )] and (4‐Py)3 PE [E = S (6 ), Se (7 )], quantitatively form complexes with ZnTPP by selective coordination of all three pyridyl groups of a molecular unit to three metalloporphyrin moieties. The formation of these complexes in chlorinated solvents is unambiguously proven by spectroscopic methods (i.e., multinuclear NMR and UV/Vis spectroscopy). The affinity of these ligands towards ZnTPP is different in benzene, yielding a mixture of products in solution. Abstract : Tri(3‐pyridyl)‐ and tri(4‐pyridyl)phosphine chalcogenides are multidentate proligands that can coordinate both through the nitrogen donors of the pyridyl moieties and the chalcogen atom on phosphorus. Owing to the significant difference in donor character, compounds from this class can be used as spacers in monomeric or polymeric heterometallic complexes.