Investigation of the Coordination Behavior of P₄S₃ towards CuBr

Abstract

The formation of coordination polymers from copper(I) bromide and P4S3, a potentially tetradentate P‐donor bridging ligand, was studied. Whereas (P4S3)3(CuBr)7 (1) formed in excellent yield, (P4S3)(CuBr)3 (2) and (P4S3)(CuBr) (3) crystallized as mixtures. The new compounds were characterized by X‐ray crystallography and solid‐state 31P MAS NMR spectroscopy. The structure of 1 consists of a 3D network of cylindrical (CuBr)n columns, castellated (CuBr)n chains and diatomic CuBr units. These building blocks are linked by tetradentate P4S3 molecules. The structure of 2 comprises undulated (CuBr)n layers, which are intra‐ and interlayer linked by tridentate P4S3 molecules. Compound 3 is a one‐dimensional polymer composed of four‐membered Cu2Br2 rings, which are bridged by the P3 bases of two P4S3 molecules.

A New Building Block for Organometallic–Inorganic Hybrid Polymers: The Mixed Group 15/16 Element Ligand Complex [Cp*2Mo2(μ,η2:2‐PSe)2(μ‐Se)] (Cp* = C5Me5)

“…The competitive coordination of copper towards P and Se sites is completed by weak intermolecular Se···Se interactions leading to the formation of two-dimensional networks. Although the coordination behavior of P 4 S 3 [17] and P 4 Se 3 [18] towards copper(I) halides has been investigated, the simultaneous coordination of 1 and P 4 Se 3 at Cu I centers opens a new route to the formation of organometallic-inorganic frameworks. It demonstrates that the P 4 Se 3 cage is able to serve as a cross-linking ligand similar to multiple Ndonor ligands in metal-organic frameworks.…”

Theoretical and Spectroscopic Investigation of Coordination Compounds from P4S3, Copper(I) Iodide and W(CO)5

“…The addition of M(CO) 5 fragments (M = Cr, Mo, W) to the apical phosphorus is, from a historical point of view, the most intensively studied reaction type since more than thirty years.…”

“…The coordination behavior of CuBr is not as straightforward and will be reported elsewhere. [5] Conventional solid-state techniques from the molten elements, phosphorus and sulfur, and CuI end up with the formation of (P 4 Q 4 )(CuI) 3 phases (Q = S, Se), in which β-P 4 Q 4 cage molecules are embedded in polymeric matrices of copper iodide. [6,7] No hint has been obtained for the formation of P 4 Q 3 containing phases, while CuCl or CuBr give rise to the formation of PHal 3 .…”

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The formation of a new type of organometallic-inorganic hybrid coordination polymer from P 4 S 3 ·W(CO) 5 (1) and CuI has been studied. The structure of {P 4 S 3 ·W(CO) 5 }(CuI) (3) has been verified by the combination of spectroscopic (IR, Raman, 31 P MAS NMR) and X-ray diffraction methods.

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“…The structure of {P 4 S 3 ·W(CO) 5 }(CuI) (3) has been verified by the combination of spectroscopic (IR, Raman, 31 P MAS NMR) and X-ray diffraction methods. Theoretical studies of β-P 4 S 3 , P 4 S 3 ·W(CO) 5 (1), 1D-(P 4 S 3 )(CuI) (2), and 3D-(P 4 S 3 )(CuI) 3 (4), which may be considered as poten- …”