Substituted aromatic pentaphosphole ligands – a journey across the p-block

Abstract

The reactivity of cationic electrophiles towards pentaphosphaferrocene [Cp*Fe(ƞ5-P5)] is explored. We report P–E bond formation for electrophiles across the p-block, producing coordination complexes with unprecedented hetero-bispentaphosphole and hetero-pentaphosphole ligands.

Snapshots of sequential polyphosphide rearrangement upon metallatetrylene addition

“…The 31 P{ 1 H} NMR spectrum of 1 reveals three sets of multiplets for the five P atoms, an apparent AA′MM′X spin system, which is typical for envelope-shaped cyclo -P 5 rings. 13 b,c ,14,15,21 Simulations of the 31 P{ 1 H} NMR spectra were performed using gNMR simulation software 22 by an iterative fitting process (Fig. 2 and see ESI, S21‡).…”

“…The reactivity towards a low-valent p-block compound was discovered recently ( Scheme 1 ), this can be accompanied by selective substitution and insertion reactions. 14 For example, when using Si( i ) or Si( ii ) species, selective insertion and substitution reactions of the cyclo -P 5 moiety are observed, leading to unusual [4 + 1] fragmentation ( cyclo -SiP 4 SiP) or Si–P substitution ( cyclo -SiP 4 ) ring products ( Scheme 1a ). 15 Using different Al( i ) nucleophiles, either an Al-functionalized bent cyclo -P 5 moiety or a cage-type structural motif was observed, the latter one was formed by [4 + 1] fragmentation ( Scheme 1a ).…”

“…16 Molecular main group polypnictogenides are indeed an interesting class of compounds with growing interests. However, the reactivity of [Cp*Fe( η 5 -E 5 )] (E = P, As) with low-valent p-block compounds is still limited, 14–17 and most of the examples only utilizing monometallic/mononuclear reagents.…”

Transformation of the cyclo‐P5 Middle Deck in [(Cp*Fe)(Cp’’’Co)(μ,η5:η4‐P5)] upon Functionalization – A Comprehensive Study of Reactivity

“…Crystallographic Data: Deposition Number(s) 2207484 (2), 2207485 (3), 2207486 (4), 2207487 (5), 2207488 (6), 2207489 (7), 2207490 (8), 2207491 (9), 2207492 (10), 2207493 (11), 2207494 (12), 2207495 (13) and 2207496 ( 14) contain(s) the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service.…”

25 years of NICS - much more than nothing!

“…The convenience while applying (vide supra) is sure a very big advantage, especially in combination with a probe not altering the system. The other huge plus for NICS is the wide range of application in organic, [22][23][24][25][26][27][28][29][30] inorganic, [31][32][33][34][35] metal clusters, [36][37][38] carbon-materials, [39][40][41] supramolecular chemistry, [42][43][44][45] bio related chemistry, [46][47][48][49] porphyrine chemistry, [50][51][52][53] chemistry of taylor-made properties, 54 polymer chemistry 55,56 etc. and these topics can again be divided into sub topics, e.g., in organic chemistry like reaction mechanism with aromatic transition states, 8,57,58 Möbius- [59][60][61] and Craig-Möbius 62-65 aromatic systems, chelate systems 66 or to metalla aromatic systems, 65,[67][68]…”