True square planar [M{N(SePⁱPr₂)₂-Se,Se′}₂] [M = Sn, Se] complexes. An extraordinary geometrical arrangement for well known centers [Sn(ii), Se(ii)]

Abstract

The syntheses and molecular structures of [M{N(SeP(i)Pr2)2-Se,Se'}2][M = Sn(2), Se(3)] are described, these complexes consist of discrete, monomeric molecules featuring MSe4 cores that comprise true square-planar geometries.

Do planar tetracoordinate tin complexes really exist?

“…11 (2) The reported Sn-Se bond lengths for 1-sq and 2-sq are in the range of 2.64-2.66 Å, which are statistically identical to the reported Se-Se bond lengths found in the true square selenium complexes, 3-sq 12 and 4-sq. 10 Furthermore, the Sn-Se bond lengths in the tetragonal tetracoordinate Sn complex, 1-tet, are significantly longer than those reported for 1-sq and 2-sq.…”

“…1 and 2), were reported. 9,10 Intriguingly, 1-sq and 2-sq possess electronegative atoms around the tin centre, opposite to their ptC congeners. Moreover, a careful inspection of both structures determined by X-ray diffraction shows the following inconsistencies:…”

Oxygen, sulfur, selenium and tellurium

“…50 We focus now on the co-ordination chemistry of chalcogen donor ligands, beginning with phosphorus chalcogenides. The first ditelluroimidodiphosphinate complexes were reported: Na[N(Pr 53 The formation of zinc phosphate polymers from insertion reactions of metathiophosphates into zinc dialkyldithiophosphates was explored using molecular simulation techniques, 54 the reaction between [Cu(MeCN) 4 ][BF 4 ], dppm and dialkyldithiophosphates affords polynuclear copper(I) complexes with bridging diphosphine ligands. 55 A macrocyclic silver(I) complex [Ag 12 (PhS 2 P-PS 2 Ph) 6 (dppeS) 6 ] was generated upon oxidation of the one-dimensional co-ordination polymer [{Ag 2 (PhS 2 P-PS 2 Ph)(dppe)} Á dppe], 56 complexes containing tripodal [AnPOS 2 ] 2and [AnPS 3 ] 2ligands were synthesised from metal alkoxides and carboxylates using Lawesson's Reagent.…”

Κρυσταλλογραφικός, φασματοσκοπικός (IR, 57Fe Moessbauer, EPR) και μαγνητικός χαρακτηρισμός πολυπυρηνικών συμπλόκων μεταλλοϊόντων μεταπτώσεως και λανθανίδων

“…Ζ δφλεζε ηάζεο ηεο νκάδαο P-Se ζεκεηψλεηαη ζηα 423 cm -1 έλαληη ησλ 488 cm -1 ηνπ ππνθαηαζηάηε. P 2 1 /c) (64) . Αμηνζεκείσην είλαη ην φηη ελψ θαηά ηηο αζχκκεηξεο δνλήζεηο ηάζεο ε ζπρλφηεηα ζπληνληζκνχ απμάλεη θαηά ηε κεηάβαζε απφ ην επίπεδν ηεηξαγσληθφ ζην ηεηξαεδξηθφ ζχκπινθν, ε ζπκκεηξηθή δφλεζε ηάζεο ηεο P-N-P νκάδαο ειαηηψλεηαη απφ ηα 790 cm -1 ζηα 770 cm -1 .…”

“…Γέθα ρξόληα αξγόηεξα, ν R. Cea-Olivares(64) ζπλέζεζε ην ζύκπινθν Sn{N(SeP i Pr 2 ) 2 } 2 , ρήκα 36, ην νπνίν θαη πάιη βξέζεθε ηεηξαγσληθό. ην ζπγθεθξηκέλν ζύκπινθν, ε γσλία Ρ-Ν-Ρ βξέζεθε 142°, πνιύ κεγαιύηεξε από 2 P(Se)NP(Se)iPr 2 ] 2 θαη Ni[Ph 2 P(Se)NPPh 2 ] 2 , ε ζπιινγή δεδνκέλσλ έγηλε ζην δηπιό πεξηζιαζίκεηξν ηεζζάξσλ Crystal Logic ρξεζηκνπνηώληαο αθηηλνβνιία ΜνΚα (ι = 0.71073 Å) (ΔΚΔΦΔ Γεκόθξηηνο).…”