Synthesis and Structure of a 1‐Phospha‐2‐boraacenaphthene Derivative and Its Chalcogenation Reactions

Abstract

The first stable 1-phospha-2-boraacenaphthene 1 was synthesized by the reduction of 1-dimesitylboryl-8-dichlorophosphinonaphthalene (2a) with elemental magnesium, and it was fully characterized. The chalcogenation reaction of 1 with elemental sulfur or selenium afforded the unique heterocycles, 2-thia- and 2-selena-1-phospha-3-boraphenalenes 9S and 9Se, respectively, through the insertion of the chalcogen atom into a P-B bond of 1. Further chalcogenation of 9 afforded the corresponding phosphine chalcogenides. These newly obtained chalcogenated compounds have been characterized. The unique dynamic behavior of 2-chalcogena-1-phospha-3-boraphenalene-1-chalcogenides 10 in solution has also been described.

Insights into Frustrated and Regular peri‐Substituted (Ace‐)Naphthylaminoboranes and (Ace‐)Naphthylphosphinoboranes

“…The molecular structures of 13 – 16 , established by single‐crystal X‐ray diffraction crystallography, are shown in Figure , and selected bond parameters are collected in Table . All compounds comprise regular Lewis pairs with short P–B peri distances between 1.978(4) Å ( 13 ) and 2.060(8) Å ( 16 ), which compares well with the P–B distance of the related dichloroborane 5‐Ph 2 P‐Ace‐6‐BCl 2 [ 12 , 2.040(2) Å] . The bulkier substituents at the B atom show slightly larger peri distances, in the order: 16 [2.060(8) Å] > 15 [2.057(2) Å] > 14 [1.996(2) Å] > 13 [1.978(4) Å].…”

“…Interestingly, the topological bond analysis revealed no principal difference between attractive and enforced B–P bonds in (ace‐)naphthylphosphinoboranes. The new acenaphthylphosphinoboranes 13 – 16 , bearing functionality at the B atom, might be of interest as starting materials for the synthesis of compound classes, such as P 2 B 2 heterocycles,, borenium ions,, , and boron‐centered radicals …”

Probing Donor–Acceptor Interactions inperi-Substituted Diphenylphosphinoacenaphthyl–Element Dichlorides of Group 13 and 15 Elements

“…Inspection of the E−P peri distances of 1−9 reveals some unexpected trends. The B−P distance of 1 (2.040(2) Å) compares well with those of the related phosphinoboranes Ia (2.108(2) Å), 3,4 IIa (2.173(3) Å), IIb (2.011(2) Å), 5 and IIIa (2.162(2) Å). 6,7 However, the Al−P distance of 2 (2.4305(5) Å) is exceptionally longer than expected; it is slightly longer than the Ga−P distance of 3 (2.411(2) Å) and even substantially longer than the P−P distance of 6 (2.252(1) Å).…”

Single Oxygen‐Atom Insertion into PB Bonds: On‐ and Off‐Metal Transformation of a Borylphosphine into a Borylphosphinite

“…Peroxides will insert O atoms into the CC bond of ketones to give esters (the Bayer–Villiger reaction9) and amine‐oxides10 have been used for oxygen insertion into SiSi,11 CB,12 BB13 and BRu14 bonds. The insertion of S and Se atoms into PB bonds of 1‐phospha‐2‐bora‐acenaphthene has been previously reported15 but, in other cases, elemental chalcogens have been shown to react with compounds containing PB bonds to give P V products 16…”