Functionalization of tetraphosphido ligands by heterocumulenes

Sebastian Hauer; Gábor Balázs; Fabian Gliese; Florian Meurer; Thomas M. Horsley Downie; Christoph Hennig; Jan J. Weigand; Robert Wolf

doi:10.1021/acs.inorgchem.4c00808

Functionalization of tetraphosphido ligands by heterocumulenes

Sebastian Hauer, Gábor Balázs, Fabian Gliese, Florian Meurer, Thomas M. Horsley Downie, Christoph Hennig, Jan J. Weigand, Robert Wolf

Pure And Applied Chemistry

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Abstract

Although numerous polyphosphido complexes have been accessed through the transition-metal-mediated activation and functionalization of white phosphorus (P₄), the selective functionalization of the resulting polyphosphorus ligands in these compounds remains underdeveloped. In this study, we explore the reactions between cyclotetraphosphido cobalt complexes and heterocumulenes, leading to functionalized P₄ ligands. Specifically, the reaction of carbon disulfide (CS₂) with [K(18c-6)][(Ar*BIAN)Co(η⁴-P₄)] ([K(18c-6)]1, 18c-6 = [18]crown-6) affords the adduct [K(18c-6)][(Ar*BIAN)Co(η³:η¹-P₄CS₂)] ([K(18c-6)]3), in which CS₂ is attached to a single phosphorus atom (Ar* = 2,6-dibenzhydryl-4-isopropylphenyl, BIAN = 1,2-bis(arylimino)acenaphthene diimine). In contrast, the insertion of bis(trimethylsilyl)sulfur diimide S(NSiMe₃)₂ into a P–P bond of [K(18c-6)]1 yields [K(18c-6)][(Ar*BIAN)Co(η³:η¹-P₄SN₂(SiMe₃)₂)] (K(18c-6)]4). This salt further reacts with Me₃SiCl to form [(Ar*BIAN)Co(η³:η¹-P₄SN₂(SiMe₃)₃] (5), featuring a rare azatetraphosphole ligand. Moreover, treatment of the previously reported complex [(Ar*BIAN)Co(η³:η¹-P₄C(O)tBu)] (2) with isothiocyanates results in P–C bond insertion, yielding [(Ar*BIAN)Co(η³:η¹-P₄C(S)N(R)C(O)tBu)] (6a,b; R = Cy, Ph).

Original language	English
Pages (from-to)	20141-20152
Number of pages	12
Journal	Inorganic Chemistry
Volume	63
Issue number	43
Early online date	31 May 2024
DOIs	https://doi.org/10.1021/acs.inorgchem.4c00808
Publication status	Published - 28 Oct 2024

Funding

We thank Dietmar Stalke (University of Go\u0308ttingen) for a generous loan of S(N tBu) and Lisa Zimmermann (University of Regensburg) for assistance with IR measurements. Florian Meurer thanks the Studienstiftung des Deutschen Volkes for his Ph.D. fellowship. Financial support of this work by the Deutsche Forschungsgemeinschaft (DFG, grants WE4621/3-2 and WO1496/7-2) and the European Research Council (ERC CoG 772299) is gratefully acknowledged. We acknowledge the European Synchrotron Radiation Facility (ESRF) for the provision of synchrotron radiation facilities by using the ROBL beamline (BM20). 2

Keywords

cyclotetraphosphido ligands
cobalt complexes
heterocumulenes

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Hauer-etal-IO-2024-Functionalization-of-tetraphosphido-ligands-by-heterocumulenesFinal published version, 4.2 MBLicence: CC BY 4.0

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@article{be16928f88184050af2166d74251a1af,

title = "Functionalization of tetraphosphido ligands by heterocumulenes",

abstract = "Although numerous polyphosphido complexes have been accessed through the transition-metal-mediated activation and functionalization of white phosphorus (P4), the selective functionalization of the resulting polyphosphorus ligands in these compounds remains underdeveloped. In this study, we explore the reactions between cyclotetraphosphido cobalt complexes and heterocumulenes, leading to functionalized P4 ligands. Specifically, the reaction of carbon disulfide (CS2) with [K(18c-6)][(Ar*BIAN)Co(η4-P4)] ([K(18c-6)]1, 18c-6 = [18]crown-6) affords the adduct [K(18c-6)][(Ar*BIAN)Co(η3:η1-P4CS2)] ([K(18c-6)]3), in which CS2 is attached to a single phosphorus atom (Ar* = 2,6-dibenzhydryl-4-isopropylphenyl, BIAN = 1,2-bis(arylimino)acenaphthene diimine). In contrast, the insertion of bis(trimethylsilyl)sulfur diimide S(NSiMe3)2 into a P–P bond of [K(18c-6)]1 yields [K(18c-6)][(Ar*BIAN)Co(η3:η1-P4SN2(SiMe3)2)] (K(18c-6)]4). This salt further reacts with Me3SiCl to form [(Ar*BIAN)Co(η3:η1-P4SN2(SiMe3)3] (5), featuring a rare azatetraphosphole ligand. Moreover, treatment of the previously reported complex [(Ar*BIAN)Co(η3:η1-P4C(O)tBu)] (2) with isothiocyanates results in P–C bond insertion, yielding [(Ar*BIAN)Co(η3:η1-P4C(S)N(R)C(O)tBu)] (6a,b; R = Cy, Ph).",

keywords = "cyclotetraphosphido ligands, cobalt complexes, heterocumulenes",

author = "Sebastian Hauer and G{\'a}bor Bal{\'a}zs and Fabian Gliese and Florian Meurer and {Horsley Downie}, {Thomas M.} and Christoph Hennig and Weigand, {Jan J.} and Robert Wolf",

year = "2024",

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doi = "10.1021/acs.inorgchem.4c00808",

language = "English",

volume = "63",

pages = "20141--20152",

journal = "Inorganic Chemistry",

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TY - JOUR

T1 - Functionalization of tetraphosphido ligands by heterocumulenes

AU - Hauer, Sebastian

AU - Balázs, Gábor

AU - Gliese, Fabian

AU - Meurer, Florian

AU - Horsley Downie, Thomas M.

AU - Hennig, Christoph

AU - Weigand, Jan J.

AU - Wolf, Robert

PY - 2024/10/28

Y1 - 2024/10/28

N2 - Although numerous polyphosphido complexes have been accessed through the transition-metal-mediated activation and functionalization of white phosphorus (P4), the selective functionalization of the resulting polyphosphorus ligands in these compounds remains underdeveloped. In this study, we explore the reactions between cyclotetraphosphido cobalt complexes and heterocumulenes, leading to functionalized P4 ligands. Specifically, the reaction of carbon disulfide (CS2) with [K(18c-6)][(Ar*BIAN)Co(η4-P4)] ([K(18c-6)]1, 18c-6 = [18]crown-6) affords the adduct [K(18c-6)][(Ar*BIAN)Co(η3:η1-P4CS2)] ([K(18c-6)]3), in which CS2 is attached to a single phosphorus atom (Ar* = 2,6-dibenzhydryl-4-isopropylphenyl, BIAN = 1,2-bis(arylimino)acenaphthene diimine). In contrast, the insertion of bis(trimethylsilyl)sulfur diimide S(NSiMe3)2 into a P–P bond of [K(18c-6)]1 yields [K(18c-6)][(Ar*BIAN)Co(η3:η1-P4SN2(SiMe3)2)] (K(18c-6)]4). This salt further reacts with Me3SiCl to form [(Ar*BIAN)Co(η3:η1-P4SN2(SiMe3)3] (5), featuring a rare azatetraphosphole ligand. Moreover, treatment of the previously reported complex [(Ar*BIAN)Co(η3:η1-P4C(O)tBu)] (2) with isothiocyanates results in P–C bond insertion, yielding [(Ar*BIAN)Co(η3:η1-P4C(S)N(R)C(O)tBu)] (6a,b; R = Cy, Ph).

AB - Although numerous polyphosphido complexes have been accessed through the transition-metal-mediated activation and functionalization of white phosphorus (P4), the selective functionalization of the resulting polyphosphorus ligands in these compounds remains underdeveloped. In this study, we explore the reactions between cyclotetraphosphido cobalt complexes and heterocumulenes, leading to functionalized P4 ligands. Specifically, the reaction of carbon disulfide (CS2) with [K(18c-6)][(Ar*BIAN)Co(η4-P4)] ([K(18c-6)]1, 18c-6 = [18]crown-6) affords the adduct [K(18c-6)][(Ar*BIAN)Co(η3:η1-P4CS2)] ([K(18c-6)]3), in which CS2 is attached to a single phosphorus atom (Ar* = 2,6-dibenzhydryl-4-isopropylphenyl, BIAN = 1,2-bis(arylimino)acenaphthene diimine). In contrast, the insertion of bis(trimethylsilyl)sulfur diimide S(NSiMe3)2 into a P–P bond of [K(18c-6)]1 yields [K(18c-6)][(Ar*BIAN)Co(η3:η1-P4SN2(SiMe3)2)] (K(18c-6)]4). This salt further reacts with Me3SiCl to form [(Ar*BIAN)Co(η3:η1-P4SN2(SiMe3)3] (5), featuring a rare azatetraphosphole ligand. Moreover, treatment of the previously reported complex [(Ar*BIAN)Co(η3:η1-P4C(O)tBu)] (2) with isothiocyanates results in P–C bond insertion, yielding [(Ar*BIAN)Co(η3:η1-P4C(S)N(R)C(O)tBu)] (6a,b; R = Cy, Ph).

KW - cyclotetraphosphido ligands

KW - cobalt complexes

KW - heterocumulenes

U2 - 10.1021/acs.inorgchem.4c00808

DO - 10.1021/acs.inorgchem.4c00808

M3 - Article

SN - 0020-1669

VL - 63

SP - 20141

EP - 20152

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 43

ER -

Functionalization of tetraphosphido ligands by heterocumulenes

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