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Dichlorobis(triphenylphosphine)nickel(II)
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<h2 id="synthesis-and-structure">Synthesis and structure</h2> <p>The blue isomer is prepared by treating hydrated <a href="/facts/Nickel_chloride/KWLuUr0V">nickel chloride</a> with <a href="/facts/Triphenylphosphine/nYFNCVcJ">triphenylphosphine</a> in alcohols or glacial <a href="/facts/Acetic_acid/uyBKA2Pd">acetic acid</a>:<a class="footnote-ref" id="fnref:2" href="#fn:2"><sup>2</sup></a> </p> NiCl2•6H2O + 2 PPh3 → NiCl2(PPh3)2 + 6 H2O <p>When allowed to crystallise from chlorinated solvents, the <a href="/facts/Tetrahedral/7mkSrl6j">tetrahedral</a> isomer converts to the square planar isomer. </p><p>The <a href="/facts/Square_planar/2mLqCvd0">square planar</a> form is red and diamagnetic. The phosphine ligands are <a href="/facts/Cis%25E2%2580%2593trans_isomerism/vqlchJly">trans</a> with respective Ni-P and Ni-Cl distances of 2.24 and 2.17 Å.<a class="footnote-ref" id="fnref:3" href="#fn:3"><sup>3</sup></a><a class="footnote-ref" id="fnref:4" href="#fn:4"><sup>4</sup></a> The blue form is paramagnetic and features tetrahedral Ni(II) centers. In this isomer, the Ni-P and Ni-Cl distances are elongated at 2.32 and 2.21 Å.<a class="footnote-ref" id="fnref:5" href="#fn:5"><sup>5</sup></a><a class="footnote-ref" id="fnref:6" href="#fn:6"><sup>6</sup></a> </p><p>As illustrated by the title complexes, tetrahedral and square planar isomers coexist in solutions of various four-coordinated nickel(II) complexes. Weak field ligands, as judged by the <a href="/facts/Spectrochemical_series/cVMy6RK4">spectrochemical series</a>, favor tetrahedral geometry and strong field ligands favor the square planar isomer. Both weak field (Cl−) and strong field (PPh3) ligands comprise NiCl2(PPh3)2, hence this compound is borderline between the two geometries. <a href="/facts/Steric_effect/TnX5c8HG">Steric effects</a> also affect the equilibrium; larger ligands favoring the less crowded tetrahedral geometry.<a class="footnote-ref" id="fnref:7" href="#fn:7"><sup>7</sup></a> </p> <h2 id="applications">Applications</h2> <p>The complex was first described by <a href="/facts/Walter_Reppe/ymWkKRod">Walter Reppe</a> who popularized its use in <a href="/facts/Alkyne_trimerisation/7pDT3SKB">alkyne trimerisations</a> and <a href="/facts/Carbonylation/Jq8jghNR">carbonylations</a>.<a class="footnote-ref" id="fnref:8" href="#fn:8"><sup>8</sup></a> Dichlorobis(triphenylphosphine)nickel(II) is a catalyst in <a href="/facts/Suzuki_reaction/aRISucCH">Suzuki reactions</a>, although usually inferior in terms of activity.<a class="footnote-ref" id="fnref:9" href="#fn:9"><sup>9</sup></a> </p> <h2 id="see-also">See also</h2> <ul><li><a href="/facts/Bis(triphenylphosphine)palladium(II)_chloride/vCGXw5CC">Bis(triphenylphosphine)palladium(II) chloride</a></li> <li><a href="/facts/Bis(triphenylphosphine)platinum(II)_chloride/9aAgVbkn">Bis(triphenylphosphine)platinum(II) chloride</a></li> <li>Bis(tricyclohexylphosphine)nickel(II) chloride<a class="footnote-ref" id="fnref:10" href="#fn:10"><sup>10</sup></a></li> <li><a href="/facts/Dichloro(1%2c2-bis(diphenylphosphino)ethane)nickel/HIaB6PpM">Dichloro(1,2-bis(diphenylphosphino)ethane)nickel</a></li></ul> <h2 id="references">References</h2> <ol> <li id="fn:1"><p>Montgomery, J. Science of Synthesis Georg Thiene Verlag KG, Vol. 1, p 11, CODEN: SSCYJ9 <a href="#fnref:1" class="footnote-back-ref">↩</a></p></li> <li id="fn:2"><p>Montgomery, J. Science of Synthesis Georg Thiene Verlag KG, Vol. 1, p 11, CODEN: SSCYJ9 <a href="#fnref:2" class="footnote-back-ref">↩</a></p></li> <li id="fn:3"><p>Batsanov, Andrei S.; Howard, Judith A. K. (2001). "trans-Dichlorobis(triphenylphosphine)nickel(II) bis(dichloromethane) solvate: redetermination at 120 K". Acta Crystallogr E. 57 (7): 308–309. Bibcode:2001AcCrE..57M.308B. doi:10.1107/S1600536801008741. S2CID 97381117. <a href="/wiki/Bibcode_(identifier)" target="_blank">/wiki/Bibcode_(identifier)</a> <a href="#fnref:3" class="footnote-back-ref">↩</a></p></li> <li id="fn:4"><p>Corain, B.; Longato, B.; Angeletti, R.; Valle, G. (1985). "trans:-[Dichlorobis(triphenylphosphine)nickel(II)]·(C2H4Cl2)2 a clathrate of the allogon of venanzi's tetrahedral complex". Inorg. Chim. Acta. 104: 15–18. doi:10.1016/S0020-1693(00)83780-9. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:4" class="footnote-back-ref">↩</a></p></li> <li id="fn:5"><p>Garton, G.; Henn, D. E.; Powell, H. M.; Venanzi, L. M. (1963). "Tetrahedral nickel(II) complexes and the factors determining their formation. Part V. The tetrahedral co-ordination of nickel in dichlorobistriphenylphosphinenickel". J. Chem. Soc. 1963: 3625–3629. doi:10.1039/JR9630003625. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:5" class="footnote-back-ref">↩</a></p></li> <li id="fn:6"><p>Brammer, L.; Stevens, E. D. (1989). "Structure of dichlorobis(triphenylphosphine)nickel(II)". Acta Crystallogr C. 45 (3): 400–403. Bibcode:1989AcCrC..45..400B. doi:10.1107/S0108270188011692. <a href="/wiki/Bibcode_(identifier)" target="_blank">/wiki/Bibcode_(identifier)</a> <a href="#fnref:6" class="footnote-back-ref">↩</a></p></li> <li id="fn:7"><p>Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 978-0-08-037941-8. <a href="978-0-08-037941-8" target="_blank">978-0-08-037941-8</a> <a href="#fnref:7" class="footnote-back-ref">↩</a></p></li> <li id="fn:8"><p>Reppe, Walter; Sweckendiek, Walter (1948). "Cyclisierende Polymerisation von Acetylen. III Benzol, Benzolderivate und hydroaromatische Verbindungen". Justus Liebigs Annalen der Chemie. 560 (1): 104–16. doi:10.1002/jlac.19485600104. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:8" class="footnote-back-ref">↩</a></p></li> <li id="fn:9"><p>Han, Fu-She (2013). "Transition-metal-catalyzed Suzuki–Miyaura cross-coupling reactions: A Remarkable Advance from Palladium to Nickel Catalysts". Chemical Society Reviews. 42 (12): 5270–98. doi:10.1039/c3cs35521g. PMID 23460083. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:9" class="footnote-back-ref">↩</a></p></li> <li id="fn:10"><p>Quasdorf, Kyle W.; Garg, Neil K. (2010). "Bis(tricyclohexylphosphine)dichloronickel". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rn01201. ISBN 978-0-471-93623-7. <a href="978-0-471-93623-7" target="_blank">978-0-471-93623-7</a> <a href="#fnref:10" class="footnote-back-ref">↩</a></p></li> </ol>