Experimental Studies on the trans‐Influence of Boryl Ligands in Square‐Planar Platinum(II) Complexes

Abstract

A series of platinum(II) boryl complexes of general formula trans-[(Cy(3)P)2Pt(Br)(BX2)], including the rare dibromoboryl species trans-[(Cy(3)P)2Pt(Br)(BBr2)], were synthesized by oxidative addition of the B-Br bond of a number of bromoboranes to [Pt(PCy3)2]. X-ray diffraction studies were performed on several such compounds. Comparison of the Pt--Br bond lengths allowed an empirical assessment of the trans-influence of different boryl ligands. A trans-influence scale was thus deduced and the results were compared with those previously computed for compounds of the type trans-[(Me(3)P)2Pt(Cl)(BX2)].

Synthesis, structure and reactivity of complexes containing a transition metal–bismuth bond

“…The expected distorted pyramidal structure at bismuth was observed, the Cl-Bi-Cl angle (95.63(3) • ) indicating significant p-orbital character in the bonding. The Pt-Cl bond distance (2.4155(9)Å) could be used to determine the strength of the trans-influence exerted by the -BiCl 2 ligand, which was observed to be weak in comparison to those exerted by a series of boryl ligands [192][193][194][195][196][197] (Scheme 23).…”

Neutral and Anionic Transition‐Metal‐Base‐Stabilized Metalloborylene Complexes

“…Notably, all three metal-boron distances are comparable to those found in iron borylene [15,16] and chromium borylene [17,18] species, thus indicating a non-negligible amount of multiple-bond character. The Pt À B bond length of 2.052(3) is rather long and exceeds those commonly found in Pt-boryl complexes, [19,20] thus being comparable to a value of 2.158(4) found for the dative interaction between platinum and boron in the aforementioned trinuclear species 6 a.…”

Cyclodimerisierung eines Oxoborylkomplexes durch trans‐Ligandabstraktion

“…80 ppm). [24] Vor diesem Hintergrund ist das 11 B-NMR-Signal von 6 vergleichbar mit denen von 1,3,2,4-Dioxodiboretanen (d = 28-43 ppm), [9,10] was auf die Bildung des Cyclodimerisierungsprodukts [(Cy 3 P) 2 Die Ergebnisse der Röntgenstrukturanalyse an einem gelben Einkristall, der durch Kühlen einer DichlormethanHexan-Lösung von 6 auf À35 8C erhalten wurde, belegen die vorgeschlagene Konstitution (Abbildung 2). [27] Der Dioxodiboretandiyl-Ligand verbrückt zwei kationische, verzerrt Tförmig koordinierte Platinzentren (P-Pt-P 167.52(6) und 169.94(6)8).…”