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Durham Research Online Durham Research Online Deposited in DRO: 10 April 2018 Version of attached le: Published Version Peer-review status of attached le: Peer-reviewed Citation for published item: Gilliard, Jr., Robert J. and Heift, Dominikus and Benko, Zoltan and Keiser, Jerod M. and Rheingold, Arnold L. and Grutzmacher, Hansjorg and Protasiewicz, John D. (2018) 'An isolable magnesium diphosphaethynolate complex.', Dalton transactions., 47 (3). pp. 666-669. Further information on publisher's website: https://doi.org/10.1039/c7dt04539e Publisher's copyright statement: This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Additional information: Use policy The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that: • a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders. Please consult the full DRO policy for further details. Durham University Library, Stockton Road, Durham DH1 3LY, United Kingdom Tel : +44 (0)191 334 3042 | Fax : +44 (0)191 334 2971 https://dro.dur.ac.uk Dalton Transactions View Article Online COMMUNICATION View Journal | View Issue An isolable magnesium diphosphaethynolate complex†‡ Cite this: Dalton Trans., 2018, 47, 666 Robert J. Gilliard, Jr., a,b Dominikus Heift, b,c Zoltán Benkő, d Jerod M. Keiser, a Received 1st December 2017, e b a Accepted 7th December 2017 Arnold L. Rheingold, Hansjörg Grützmacher * andJohnD.Protasiewicz * DOI: 10.1039/c7dt04539e rsc.li/dalton The reaction of magnesium chloride with two equivalents of sodium phosphaethynolate, Na[OCP]·(dioxane)2.5 (1), yields a mag- nesium diphosphaethynolate complex, [(THF)4Mg(OCP)2] (3). The formation of compound 3 goes through a monosubstituted chlor- omagnesium phosphaethynolate Mg(OCP)Cl (2). The structure of 3 was determined via a single crystal X-ray diffraction study. For Creative Commons Attribution-NonCommercial 3.0 Unported Licence. comparison, we also report the structure of a monomeric sodium phosphaethynolate complex, [Na(OCP)(dibenzo-18-crown-6)] (4). It has been more than two decades since Becker reported the structure of lithium phosphaethynolate, [(DME)2Li(OCP)] A (Fig. 1).1 The highly reactive nature and limited stability of this compound discouraged detailed studies of the (OCP) anion. Subsequent reports discussed the challenging nature of phos- This article is licensed under a phaethynolate chemistry which was mostly attributed to the 1,2 instability and low yield of Mx(OCP)y (M = metal) salts. We recently reported a new method for the large scale preparation of sodium phosphaethynolate, Na(OCP)·(dioxane)x, spawning a 1,3,17,22 Open Access Article. Published on 08 December 2017. Downloaded 10/04/2018 14:46:07. resurgence of interest in the synthesis, structure, and reactivity Fig. 1 O-Bound metal phosphaethynolate complexes. of this 3-atom organophosphorus building block.3 Notably, Na(OCP)·(dioxane)x is a remarkably stable synthon that can be − Resonance Theory calculations have shown that (OCP) has stored under inert atmosphere indefinitely. − − three major resonance structures: [O–CuP] (51.7%), The phosphaethynolate anion, (OCP) , may be regarded as − − 4 − [OvCvP] (40.2%) and [OuC → P] (7.1%). Recently, reactiv- the phosphorus analogue of cyanate, (OCN) .3 Natural ity studies involving these salts has led to the formation of – – novel heterocycles,5 11 main-group small molecules,12 15 tran- – sition metal complexes,4,16 19 and phosphorus derivatives of aDepartment of Chemistry, Case Western Reserve University, Cleveland, OH 44106, organic molecules.20,21 However, the number of O-bound USA. E-mail: [email protected] bDepartment of Chemistry and Applied Biosciences, ETH Zurich, CH-8093 Zurich, phosphaethynolate salts are limited as most Mx(OCP)y com- 4,11–16,18,19 Switzerland. E-mail: [email protected] pounds feature M–P instead of M–O bonds. Thus, cDepartment of Chemistry, Durham University, Lower Mountjoy, South Road, the only structurally characterized examples of complexes with Durham, DH1 3LE, UK M–O–CuP functionalities are of lithium A,1 calcium B,22 dBudapest University of Technology and Economics, H.111 Budapest Szent sodium C,3 uranium D,17 and thorium E (Fig. 1).17 While the Gellért tér 4, Hungary – u A B C eDepartment of Chemistry, University of California, San Diego, La Jolla, CA 92093, O C P moiety in compounds , , and are stabilized via USA dimethoxyethane (DME) coordination, the isolation of com- †This manuscript is published in honor of Professor Phil Power’s65th birthday. pounds D and E relies on the coordination of tris-amidinate We are grateful to Phil for his service to the chemistry community. His contri- ligands. butions in synthetic inorganic chemistry continues to inspire us all. Westerhausen prepared a series of alkaline earth metal ‡Electronic supplementary information (ESI) available. CCDC 1544892 (3) and 22 1544893 (4). For ESI and crystallographic data in CIF or other electronic format phosphaethynolates. The synthesis of these compounds see DOI: 10.1039/c7dt04539e involved the reaction of alkali earth metal bis(trimethylsilyl) 666 | Dalton Trans.,2018,47, 666–669 This journal is © The Royal Society of Chemistry 2018 View Article Online Dalton Transactions Communication phosphides M[P(SiMe3)2]2 (M = Mg, Ca, Sr, Ba) with dimethyl that if 1 is added to MgCl2 too rapidly, the yield of 3 is compro- ff carbonate (MeO)2CO in DME to a ord M(OCP)x(DME)y and tri- mised and instead an insoluble dark colored precipitate is 22 methylsilylether MeOSiMe3. However, these salts were formed. Samples of solid 3 analyzed after months of storage 31 unstable, even at low temperatures. Storage of B at −30 °C under N2 showed no evidence of decomposition by P NMR resulted in the formation of single crystals, but attempts to spectroscopy. Interestingly, while Mg(OCP)2 is stable as a THF isolate the salt resulted in immediate decomposition. The adduct, if DME is added to the solid, some decomposition is structure of magnesium phosphaethynolate was formulated to observed (i.e., formation of a small amount of gray precipitate), be the cis-diphosphaethynolate [(DME)3Mg(OCP)2], however, thereby highlighting the importance of coordination chemistry samples obtained by this method could not be isolated and in the synthesis, stability, and reactivity of these salts. characterization was limited to NMR experiments. Indeed, it The X-ray structure of 3 reveals a six-coordinate magnesium has proved challenging to prepare diphosphaethynolate com- atom in an octahedral geometry and the two OCP units are plexes where two OCP units bind to the same metal center. related by a crystallographic inversion center (Fig. 2). This During our studies we have found that the formation and differs from the square antiprismatic geometry in eight-coordi- 4 B stability of Mx(OCP)y salts is highly dependent on the synthetic nate metal complexes (Fig. 3) and (Fig. 1). route and the coordination environment around the metal The Ca–OOCP bond distance in B is 2.358(2) Å, which is sig- cation. Herein, we report the synthesis, molecular structure, nificantly longer than the comparable Mg1–O1 bond in 3 and computations of a magnesium diphosphaethynolate (2.024(16) Å).22 The M–O–C angle in 3 is 142.8°, which is 1 17 17 complex, [(THF)4Mg(OCP)2](3). Notably, compound 3 is a smaller than in A (170.7°), D (170.9°), and E (176.4°), but unique example of a stable metal diphosphaethynolate more comparable to B (154.6°),22 C (132.1°),3 and 4 (138.1°). In complex that can be isolated and stored at room temperature. notable contrast to the monomeric potassium phosphaethyno- 5 The structure of compound 3 is compared to a novel [Na(OCP) late reported by Goicoechea which contains a K–PPCO bond (dibenzo-18-crown-6)] complex (4). (3.383 Å), the structure of 4 features an Na–OOCP bond Creative Commons Attribution-NonCommercial 3.0 Unported Licence. The reaction of magnesium chloride with Na[OCP]· (2.290 Å). 31 (dioxane)2.5 (1) is extremely sensitive to the reaction con- Analysis of the reaction progress by P NMR spectroscopy ditions. Our initial attempts to synthesize magnesium diphos- suggest that the formation of compound 3 goes through a phaethynolate involved the addition of a DME solution monosubstituted chloromagnesium phosphaethynolate 2. containing two equivalents of 1 to a suspension of anhydrous Accordingly, MgCl2 was reacted with various equivalents of 31 MgCl2 powder in DME at various temperatures. These reac- compound 1 in THF at room temperature and the P NMR tions failed to yield the desired diphosphaethynolate complex spectra were recorded. The spectrum of 1 in THF shows a and instead led to the formation of an insoluble gray precipi- singlet at δ = −392.9 ppm (Fig. 4a). When MgCl2 is reacted tate. However, upon slow dropwise addition of a THF solution with one equivalent of 1, a new peak at δ = −369.5 ppm is This article is licensed under a 1 1 of to a suspension of MgCl2 vigorously stirred in a formed and compound is completely consumed (Fig. 4b). THF/toluene mixture, a slightly cloudy pink solution contain- Although the structure has not been obtained, we assign this ing 3 was obtained (Scheme 1). Immediately after the addition peak as the monosubstituted Mg(OCP)Cl compound (2). 2 3 Open Access Article. Published on 08 December 2017. Downloaded 10/04/2018 14:46:07. was complete, the solution was filtered and concentrated to Significantly, compounds and can be observed upon give an off-white solid which was collected by filtration.
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