Small Molecule Activation by POC sp 3OP‐Nickel Complexes. Issue 39 (21st August 2014)

• Record Type: Journal Article
• Authors: Hao, Jingjun; Vabre, Boris; Mougang‐Soumé, Berline; Zargarian, Davit
• Is Part Of: Chemistry. Volume 20:Issue 39(2014)
• Page Start: 12544
• Page End: 12552
• Publication Date: 2014-08-21
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201402933
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>This contribution describes the reactivities of CO<sub>2</sub>, CO, O<sub>2</sub>, and ArNC with the pincer‐type complexes [(κ<sup>P</sup>, κ<sup>C</sup>, κ<sup>P′</sup>‐POC<inline-formula><alternatives><inline-graphic mimetype="image" xlink:href="ark:/27927/pgh1c448c7p" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /><mml:math altimg="urn:x-wiley:09476539:media:CHEM201402933:tex2gif-inf-4" overflow="scroll" xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mtext> </mml:mtext><mml:mrow><mml:mtext>sp</mml:mtext><mml:msup><mml:mtext> </mml:mtext><mml:mrow><mml:mtext>3</mml:mtext></mml:mrow></mml:msup></mml:mrow></mml:msub></mml:math></alternatives></inline-formula>OP)NiX] (POC<inline-formula><alternatives><inline-graphic mimetype="image" xlink:href="ark:/27927/pgh1c448c9s" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /><mml:math altimg="urn:x-wiley:09476539:media:CHEM201402933:tex2gif-inf-5" overflow="scroll" xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mtext> </mml:mtext><mml:mrow><mml:mtext>sp</mml:mtext><mml:msup><mml:mtext> </mml:mtext><mml:mrow><mml:mtext>3</mml:mtext></mml:mrow></mml:msup></mml:mrow></mml:msub></mml:math></alternatives></inline-formula>OP=(R<sub>2</sub>POCH<sub>2</sub>)<sub>2</sub>CH; R=<italic>i</italic>Pr; X=OSiMe<sub>3</sub>, NArH; Ar=2, 6‐<italic>i</italic>Pr<sub>2</sub>C<sub>6</sub>H<sub>3</sub>). Reaction of the amido derivative with CO<sub>2</sub> and CO leads to a simple insertion into the NiN bond to give stable carbamate and carbamoyl derivatives, respectively, the pincer ligand backbone remaining intact in both cases. In contrast, the analogous reactions with the siloxide derivative produced kinetically labile insertion products that either revert to the starting material (in the case of CO<sub>2</sub>) or react further to give the mixed‐valent, dinickel species [(POC<inline-formula><alternatives><inline-graphic mimetype="image" xlink:href="ark:/27927/pgh1c447d3h" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /><mml:math altimg="urn:x-wiley:09476539:media:CHEM201402933:tex2gif-inf-15" overflow="scroll" xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mtext> </mml:mtext><mml:mrow><mml:mtext>sp</mml:mtext><mml:msup><mml:mtext> </mml:mtext><mml:mrow><mml:mtext>3</mml:mtext></mml:mrow></mml:msup></mml:mrow></mml:msub></mml:math></alternatives></inline-formula>OP)Ni<sup>II</sup>{μ, κ<sup>O</sup>, κ<sup>P</sup>, κ<sup>P′</sup>‐OCOCH(CH<sub>2</sub>CH<sub>2</sub>OPR<sub>2</sub>)<sub>2</sub>}Ni<sup>0</sup>(CO)<sub>2</sub>]. The zero‐valent center in the latter compound is ligated by a new ligand arising from transformation of the POC<inline-formula><alternatives><inline-graphic mimetype="image" xlink:href="ark:/27927/pgh1c447d1d" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /><mml:math altimg="urn:x-wiley:09476539:media:CHEM201402933:tex2gif-inf-21" overflow="scroll" xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mtext> </mml:mtext><mml:mrow><mml:mtext>sp</mml:mtext><mml:msup><mml:mtext> </mml:mtext><mml:mrow><mml:mtext>3</mml:mtext></mml:mrow></mml:msup></mml:mrow></mml:msub></mml:math></alternatives></inline-formula>OP ligand backbone. The carbonylation and carboxylation of the siloxido derivative also produced minor quantities of a side‐product identified as the trinickel species, [{(η<sup>3</sup>‐allyl)Ni(μ<sup>O</sup>, κ<sup>P</sup>‐R<sub>2</sub>PO)<sub>2</sub>}<sub>2</sub>Ni], arising from total dismantling of the POC<inline-formula><alternatives><inline-graphic mimetype="image" xlink:href="ark:/27927/pgh1c447d0v" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /><mml:math altimg="urn:x-wiley:09476539:media:CHEM201402933:tex2gif-inf-25" overflow="scroll" xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mtext> </mml:mtext><mml:mrow><mml:mtext>sp</mml:mtext><mml:msup><mml:mtext> </mml:mtext><mml:mrow><mml:mtext>3</mml:mtext></mml:mrow></mml:msup></mml:mrow></mml:msub></mml:math></alternatives></inline-formula>OP ligand. Similar reactivities were observed with isonitrile, ArNC: reaction with the siloxido derivative resulted in a complex sequence of steps involving initial insertion, a 1, 3‐hydrogen shift, and an Arbuzov rearrangement to give [Ni(CNAr)<sub>4</sub>] and a methacrylamide based on fragments of the POC<inline-formula><alternatives><inline-graphic mimetype="image" xlink:href="ark:/27927/pgh1c447czs" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /><mml:math altimg="urn:x-wiley:09476539:media:CHEM201402933:tex2gif-inf-27" overflow="scroll" xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mtext> </mml:mtext><mml:mrow><mml:mtext>sp</mml:mtext><mml:msup><mml:mtext> </mml:mtext><mml:mrow><mml:mtext>3</mml:mtext></mml:mrow></mml:msup></mml:mrow></mml:msub></mml:math></alternatives></inline-formula>OP ligand. Oxygenation of the amido and siloxido derivatives led to the phosphinate derivative, [(POC<inline-formula><alternatives><inline-graphic mimetype="image" xlink:href="ark:/27927/pgh1c447cx7" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /><mml:math altimg="urn:x-wiley:09476539:media:CHEM201402933:tex2gif-inf-28" overflow="scroll" xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mtext> </mml:mtext><mml:mrow><mml:mtext>sp</mml:mtext><mml:msup><mml:mtext> </mml:mtext><mml:mrow><mml:mtext>3</mml:mtext></mml:mrow></mml:msup></mml:mrow></mml:msub></mml:math></alternatives></inline-formula>OP)Ni(OP(O)R<sub>2</sub>)], arising from oxidative transformation of the original ligand frame; the reaction with the Ni‐NHAr derivative also gave ArHNP(O)R<sub>2</sub> through a complex NP bond‐forming reaction.</p> </abstract>