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Thus, the lanthanoid pyrazolates, [Ln(Ph<jats:sub>2<\/jats:sub>pz)<jats:sub>3<\/jats:sub>(thf)<jats:sub>3<\/jats:sub>] (Ph<jats:sub>2<\/jats:sub>pz=3,5\u2010diphenylpyrazolate; Ln=La, <jats:bold>1<\/jats:bold>, Ce, <jats:bold>2<\/jats:bold>, Nd, <jats:bold>3<\/jats:bold>, Tb, <jats:bold>4<\/jats:bold>; thf=tetrahydrofuran), [Ln<jats:sub>2<\/jats:sub>(Ph<jats:sub>2<\/jats:sub>pz)<jats:sub>4<\/jats:sub>(OMe)<jats:sub>2<\/jats:sub>(dme)<jats:sub>2<\/jats:sub>]<jats:bold>\u22c5<\/jats:bold>2\u2009dme (Ln=Ho, <jats:bold>5<\/jats:bold>, Er, <jats:bold>6<\/jats:bold>, Tm, <jats:bold>7<\/jats:bold>, Lu, <jats:bold>8<\/jats:bold>; dme=1,2\u2010dimethoxyethane), [Ln(Ph<jats:sub>2<\/jats:sub>pz)<jats:sub>3<\/jats:sub>(dme)<jats:sub>2<\/jats:sub>] (Ln=Dy, <jats:bold>9<\/jats:bold>, Sm, <jats:bold>10<\/jats:bold>), [Ln(<jats:italic>t<\/jats:italic>Bu<jats:sub>2<\/jats:sub>pz)<jats:sub>3<\/jats:sub>(thf)<jats:sub>2<\/jats:sub>] (<jats:italic>t<\/jats:italic>Bu<jats:sub>2<\/jats:sub>pz=3,5\u2010di\u2010<jats:italic>tert<\/jats:italic>\u2010butylpyrazolate; Ln=La, <jats:bold>11<\/jats:bold>, Ce, <jats:bold>12<\/jats:bold>, Sm, <jats:bold>13<\/jats:bold>, Gd, <jats:bold>14<\/jats:bold>, Dy, <jats:bold>15<\/jats:bold>, Ho, <jats:bold>16<\/jats:bold>, Tm, <jats:bold>17<\/jats:bold>, Yb, <jats:bold>18<\/jats:bold>, Lu, <jats:bold>19<\/jats:bold>), [Ln(ttfpz)<jats:sub>3<\/jats:sub>(thf)<jats:sub>3<\/jats:sub>] (ttfpz<jats:bold>=<\/jats:bold>3\u2010(2\u2032\u2010thienyl)\u20105\u2010(trifluoromethyl)pyrazolate; Ln=La, <jats:bold>20<\/jats:bold>, Sm, <jats:bold>21<\/jats:bold>), and [Er(PhMepz)<jats:sub>3<\/jats:sub>(thf)<jats:sub>2<\/jats:sub>] <jats:bold>22<\/jats:bold> (PhMepz=3\u2010phenyl\u20105\u2010methylpyrazolate) have been prepared in good yields by redox transmetallation\/protolysis reactions employing lanthanoid metals and trispentafluorophenylbismuth [Bi(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub>]<jats:bold>\u22c5<\/jats:bold>0.5\u2009diox (diox=1, 4\u2010dioxane) in donor solvents. This is a new and efficient synthetic route in which Bi(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>3<\/jats:sub> replaces the commonly used Hg(C<jats:sub>6<\/jats:sub>F<jats:sub>5<\/jats:sub>)<jats:sub>2<\/jats:sub> or HgPh<jats:sub>2<\/jats:sub>, and provides proof of concept for the method. [Ln<jats:sub>2<\/jats:sub>(Ph<jats:sub>2<\/jats:sub>pz)<jats:sub>4<\/jats:sub>(OMe)<jats:sub>2<\/jats:sub>(dme)<jats:sub>2<\/jats:sub>]<jats:bold>\u22c5<\/jats:bold>2\u2009dme (<jats:bold>5<\/jats:bold>\u2013<jats:bold>8<\/jats:bold>) complexes are derived from C\u2212O bond activation of dme on crystallization of the initial products from this solvent, and are dimeric methoxide\u2010bridged species. Other structures are monomeric with \u03b7<jats:sup>2<\/jats:sup>\u2010bound pyrazolate ligands and nine\u2010coordinate metal atoms for complexes <jats:bold>1<\/jats:bold>\u2013<jats:bold>4<\/jats:bold>, <jats:bold>9<\/jats:bold>\u2013<jats:bold>10<\/jats:bold> and <jats:bold>20<\/jats:bold>\u2013<jats:bold>21<\/jats:bold>, and eight\u2010coordinate metal atoms for complexes <jats:bold>11<\/jats:bold>\u2013<jats:bold>19<\/jats:bold> and <jats:bold>22<\/jats:bold>.<\/jats:p>","DOI":"10.1002\/chem.201804703","type":"journal-article","created":{"date-parts":[[2018,10,15]],"date-time":"2018-10-15T21:49:46Z","timestamp":1539640186000},"page":"17464-17474","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["Can Bismuth Replace Mercury in Redox Transmetallation\/Protolysis Syntheses from Free Lanthanoid Metals?"],"prefix":"10.1002","volume":"24","author":[{"given":"Zhifang","family":"Guo","sequence":"first","affiliation":[{"name":"School of Chemistry Monash University  Clayton 3800 Australia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2984-6048","authenticated-orcid":false,"given":"Victoria","family":"Blair","sequence":"additional","affiliation":[{"name":"School of Chemistry Monash University  Clayton 3800 Australia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6966-6121","authenticated-orcid":false,"given":"Glen B.","family":"Deacon","sequence":"additional","affiliation":[{"name":"School of Chemistry Monash University  Clayton 3800 Australia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0683-8918","authenticated-orcid":false,"given":"Peter C.","family":"Junk","sequence":"additional","affiliation":[{"name":"College of Science &amp; Engineering James Cook University  Townsville 4811 QLD Australia"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2018,11,14]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1016\/B0-08-043748-6\/02004-1"},{"volume-title":"Alkoxo and Aryloxo Derivatives of Metals","year":"2001","author":"Bradley D. 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