Terminal Platinum(II) Phosphido Complexes: Synthesis, Structure, and Thermochemistry
A series of terminal Pt(II) phosphido complexes Pt(dppe)(Me)(PRR‘) (R = H; R‘ = Mes* (1), R‘ = Mes (2), R‘ = Ph (3), R‘ = Cy (4); R = R‘ = Mes (5); R = R‘ = Ph (6); R = R‘ = Cy (7); R = R‘ = Et (8); R = Ph, R‘ = i-Bu (9)) has been prepared by proton transfer from the appropriate phosphine to the met...
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Veröffentlicht in: | Organometallics 1998-02, Vol.17 (4), p.652-660 |
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creator | Wicht, Denyce K. Paisner, Sara N. Lew, Belinda M. Glueck, David S. Yap, Glenn P. A. Liable-Sands, Louise M. Rheingold, Arnold L. Haar, Christopher M. Nolan, Steven P. |
description | A series of terminal Pt(II) phosphido complexes Pt(dppe)(Me)(PRR‘) (R = H; R‘ = Mes* (1), R‘ = Mes (2), R‘ = Ph (3), R‘ = Cy (4); R = R‘ = Mes (5); R = R‘ = Ph (6); R = R‘ = Cy (7); R = R‘ = Et (8); R = Ph, R‘ = i-Bu (9)) has been prepared by proton transfer from the appropriate phosphine to the methoxide ligand of Pt(dppe)(Me)(OMe) (10) (dppe = Ph2PCH2CH2PPh2; Mes* = 2,4,6-(t-Bu)3C6H2; Mes = 2,4,6-Me3C6H2; Cy = cyclo-C6H11). Complexes 1 and 2 were also made by deprotonation of the cations [Pt(dppe)(Me)(PH2Ar)][BF4] (Ar = Mes* (13); Ar = Mes (14)). For comparison to 1, the arylthiolate and aryloxide complexes Pt(dppe)(Me)(EMes*) (E = S (11); E = O (12)) were also prepared from 10. NMR studies of the proton-transfer equilibria between Pt(dppe)(Me)(X), Pt(dppe)(Me)(Y), and the acids HY and HX (see Bryndza, H. E.; Fong, L. K.; Paciello, R. A.; Tam, W.; Bercaw, J. E. J. Am. Chem. Soc. 1987, 109, 1444−1456 and Bryndza, H. E.; Domaille, P. J.; Tam, W.; Fong, L. K.; Paciello, R. A.; Bercaw, J. E. Polyhedron 1988, 7, 1441−1452) provide an approximate partial ranking of Pt−P bond strengths in this series: Pt−PHPh > Pt−PHMes > Pt−PHMes*; Pt−PPh2 > Pt−PMes2. Complementary solution calorimetry investigations probe the role of entropic effects on the equilibria. Both steric and electronic factors appear to be important in controlling relative Pt−P bond strengths. The Pt−S bonds in 11 and Pt(dppe)(Me)(SPh) are stronger than the analogous Pt−P bonds in 1 and 3. Complexes 1 and 5·THF were structurally characterized by X-ray crystallography. |
doi_str_mv | 10.1021/om9708891 |
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A. ; Liable-Sands, Louise M. ; Rheingold, Arnold L. ; Haar, Christopher M. ; Nolan, Steven P.</creator><creatorcontrib>Wicht, Denyce K. ; Paisner, Sara N. ; Lew, Belinda M. ; Glueck, David S. ; Yap, Glenn P. A. ; Liable-Sands, Louise M. ; Rheingold, Arnold L. ; Haar, Christopher M. ; Nolan, Steven P.</creatorcontrib><description>A series of terminal Pt(II) phosphido complexes Pt(dppe)(Me)(PRR‘) (R = H; R‘ = Mes* (1), R‘ = Mes (2), R‘ = Ph (3), R‘ = Cy (4); R = R‘ = Mes (5); R = R‘ = Ph (6); R = R‘ = Cy (7); R = R‘ = Et (8); R = Ph, R‘ = i-Bu (9)) has been prepared by proton transfer from the appropriate phosphine to the methoxide ligand of Pt(dppe)(Me)(OMe) (10) (dppe = Ph2PCH2CH2PPh2; Mes* = 2,4,6-(t-Bu)3C6H2; Mes = 2,4,6-Me3C6H2; Cy = cyclo-C6H11). Complexes 1 and 2 were also made by deprotonation of the cations [Pt(dppe)(Me)(PH2Ar)][BF4] (Ar = Mes* (13); Ar = Mes (14)). For comparison to 1, the arylthiolate and aryloxide complexes Pt(dppe)(Me)(EMes*) (E = S (11); E = O (12)) were also prepared from 10. NMR studies of the proton-transfer equilibria between Pt(dppe)(Me)(X), Pt(dppe)(Me)(Y), and the acids HY and HX (see Bryndza, H. E.; Fong, L. K.; Paciello, R. A.; Tam, W.; Bercaw, J. E. J. Am. Chem. Soc. 1987, 109, 1444−1456 and Bryndza, H. E.; Domaille, P. J.; Tam, W.; Fong, L. K.; Paciello, R. A.; Bercaw, J. E. Polyhedron 1988, 7, 1441−1452) provide an approximate partial ranking of Pt−P bond strengths in this series: Pt−PHPh > Pt−PHMes > Pt−PHMes*; Pt−PPh2 > Pt−PMes2. Complementary solution calorimetry investigations probe the role of entropic effects on the equilibria. Both steric and electronic factors appear to be important in controlling relative Pt−P bond strengths. The Pt−S bonds in 11 and Pt(dppe)(Me)(SPh) are stronger than the analogous Pt−P bonds in 1 and 3. Complexes 1 and 5·THF were structurally characterized by X-ray crystallography.</description><identifier>ISSN: 0276-7333</identifier><identifier>EISSN: 1520-6041</identifier><identifier>DOI: 10.1021/om9708891</identifier><language>eng</language><publisher>American Chemical Society</publisher><ispartof>Organometallics, 1998-02, Vol.17 (4), p.652-660</ispartof><rights>Copyright © 1998 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a293t-2ba4a920c9a1924a55316d063391f5c2fad50de6d91619dc704dd18013967a813</citedby><cites>FETCH-LOGICAL-a293t-2ba4a920c9a1924a55316d063391f5c2fad50de6d91619dc704dd18013967a813</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/om9708891$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/om9708891$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,2765,27076,27924,27925,56738,56788</link.rule.ids></links><search><creatorcontrib>Wicht, Denyce K.</creatorcontrib><creatorcontrib>Paisner, Sara N.</creatorcontrib><creatorcontrib>Lew, Belinda M.</creatorcontrib><creatorcontrib>Glueck, David S.</creatorcontrib><creatorcontrib>Yap, Glenn P. A.</creatorcontrib><creatorcontrib>Liable-Sands, Louise M.</creatorcontrib><creatorcontrib>Rheingold, Arnold L.</creatorcontrib><creatorcontrib>Haar, Christopher M.</creatorcontrib><creatorcontrib>Nolan, Steven P.</creatorcontrib><title>Terminal Platinum(II) Phosphido Complexes: Synthesis, Structure, and Thermochemistry</title><title>Organometallics</title><addtitle>Organometallics</addtitle><description>A series of terminal Pt(II) phosphido complexes Pt(dppe)(Me)(PRR‘) (R = H; R‘ = Mes* (1), R‘ = Mes (2), R‘ = Ph (3), R‘ = Cy (4); R = R‘ = Mes (5); R = R‘ = Ph (6); R = R‘ = Cy (7); R = R‘ = Et (8); R = Ph, R‘ = i-Bu (9)) has been prepared by proton transfer from the appropriate phosphine to the methoxide ligand of Pt(dppe)(Me)(OMe) (10) (dppe = Ph2PCH2CH2PPh2; Mes* = 2,4,6-(t-Bu)3C6H2; Mes = 2,4,6-Me3C6H2; Cy = cyclo-C6H11). Complexes 1 and 2 were also made by deprotonation of the cations [Pt(dppe)(Me)(PH2Ar)][BF4] (Ar = Mes* (13); Ar = Mes (14)). For comparison to 1, the arylthiolate and aryloxide complexes Pt(dppe)(Me)(EMes*) (E = S (11); E = O (12)) were also prepared from 10. NMR studies of the proton-transfer equilibria between Pt(dppe)(Me)(X), Pt(dppe)(Me)(Y), and the acids HY and HX (see Bryndza, H. E.; Fong, L. K.; Paciello, R. A.; Tam, W.; Bercaw, J. E. J. Am. Chem. Soc. 1987, 109, 1444−1456 and Bryndza, H. E.; Domaille, P. J.; Tam, W.; Fong, L. K.; Paciello, R. A.; Bercaw, J. E. Polyhedron 1988, 7, 1441−1452) provide an approximate partial ranking of Pt−P bond strengths in this series: Pt−PHPh > Pt−PHMes > Pt−PHMes*; Pt−PPh2 > Pt−PMes2. Complementary solution calorimetry investigations probe the role of entropic effects on the equilibria. Both steric and electronic factors appear to be important in controlling relative Pt−P bond strengths. The Pt−S bonds in 11 and Pt(dppe)(Me)(SPh) are stronger than the analogous Pt−P bonds in 1 and 3. Complexes 1 and 5·THF were structurally characterized by X-ray crystallography.</description><issn>0276-7333</issn><issn>1520-6041</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1998</creationdate><recordtype>article</recordtype><recordid>eNptkE9LwzAchoMoOKcHv0EvgoNV80vapPEmZc7JwEErO4bYpLSzf0bSwnbz6tf0k1iZ7OTpvTw8vDwIXQO-A0zgvq0Fx1Ek4ASNICTYZziAUzTChDOfU0rP0YVzG4wx45SM0Do1ti4bVXmrSnVl09e3i8XEWxWt2xalbr24rbeV2Rn38P355SX7piuMK93USzrbZ11vzdRTjfbSYhC1WWHq0nV2f4nOclU5c_W3Y_T2NEvjZ3_5Ol_Ej0tfEUE7n7yrQAmCM6FAkECFIQWmMaNUQB5mJFc6xNowLYCB0BnHgdYQYaCCcRUBHaPJwZvZ1jlrcrm1Za3sXgKWv0XkscjA-gd2eGh2R1DZDznE4KFMV4mcr2POIFnLl4G_OfAqc3LT9nbI5P7x_gDjpG7i</recordid><startdate>19980216</startdate><enddate>19980216</enddate><creator>Wicht, Denyce K.</creator><creator>Paisner, Sara N.</creator><creator>Lew, Belinda M.</creator><creator>Glueck, David S.</creator><creator>Yap, Glenn P. A.</creator><creator>Liable-Sands, Louise M.</creator><creator>Rheingold, Arnold L.</creator><creator>Haar, Christopher M.</creator><creator>Nolan, Steven P.</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>19980216</creationdate><title>Terminal Platinum(II) Phosphido Complexes: Synthesis, Structure, and Thermochemistry</title><author>Wicht, Denyce K. ; Paisner, Sara N. ; Lew, Belinda M. ; Glueck, David S. ; Yap, Glenn P. A. ; Liable-Sands, Louise M. ; Rheingold, Arnold L. ; Haar, Christopher M. ; Nolan, Steven P.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a293t-2ba4a920c9a1924a55316d063391f5c2fad50de6d91619dc704dd18013967a813</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1998</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Wicht, Denyce K.</creatorcontrib><creatorcontrib>Paisner, Sara N.</creatorcontrib><creatorcontrib>Lew, Belinda M.</creatorcontrib><creatorcontrib>Glueck, David S.</creatorcontrib><creatorcontrib>Yap, Glenn P. A.</creatorcontrib><creatorcontrib>Liable-Sands, Louise M.</creatorcontrib><creatorcontrib>Rheingold, Arnold L.</creatorcontrib><creatorcontrib>Haar, Christopher M.</creatorcontrib><creatorcontrib>Nolan, Steven P.</creatorcontrib><collection>Istex</collection><collection>CrossRef</collection><jtitle>Organometallics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Wicht, Denyce K.</au><au>Paisner, Sara N.</au><au>Lew, Belinda M.</au><au>Glueck, David S.</au><au>Yap, Glenn P. A.</au><au>Liable-Sands, Louise M.</au><au>Rheingold, Arnold L.</au><au>Haar, Christopher M.</au><au>Nolan, Steven P.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Terminal Platinum(II) Phosphido Complexes: Synthesis, Structure, and Thermochemistry</atitle><jtitle>Organometallics</jtitle><addtitle>Organometallics</addtitle><date>1998-02-16</date><risdate>1998</risdate><volume>17</volume><issue>4</issue><spage>652</spage><epage>660</epage><pages>652-660</pages><issn>0276-7333</issn><eissn>1520-6041</eissn><abstract>A series of terminal Pt(II) phosphido complexes Pt(dppe)(Me)(PRR‘) (R = H; R‘ = Mes* (1), R‘ = Mes (2), R‘ = Ph (3), R‘ = Cy (4); R = R‘ = Mes (5); R = R‘ = Ph (6); R = R‘ = Cy (7); R = R‘ = Et (8); R = Ph, R‘ = i-Bu (9)) has been prepared by proton transfer from the appropriate phosphine to the methoxide ligand of Pt(dppe)(Me)(OMe) (10) (dppe = Ph2PCH2CH2PPh2; Mes* = 2,4,6-(t-Bu)3C6H2; Mes = 2,4,6-Me3C6H2; Cy = cyclo-C6H11). Complexes 1 and 2 were also made by deprotonation of the cations [Pt(dppe)(Me)(PH2Ar)][BF4] (Ar = Mes* (13); Ar = Mes (14)). For comparison to 1, the arylthiolate and aryloxide complexes Pt(dppe)(Me)(EMes*) (E = S (11); E = O (12)) were also prepared from 10. NMR studies of the proton-transfer equilibria between Pt(dppe)(Me)(X), Pt(dppe)(Me)(Y), and the acids HY and HX (see Bryndza, H. E.; Fong, L. K.; Paciello, R. A.; Tam, W.; Bercaw, J. E. J. Am. Chem. Soc. 1987, 109, 1444−1456 and Bryndza, H. E.; Domaille, P. J.; Tam, W.; Fong, L. K.; Paciello, R. A.; Bercaw, J. E. Polyhedron 1988, 7, 1441−1452) provide an approximate partial ranking of Pt−P bond strengths in this series: Pt−PHPh > Pt−PHMes > Pt−PHMes*; Pt−PPh2 > Pt−PMes2. Complementary solution calorimetry investigations probe the role of entropic effects on the equilibria. Both steric and electronic factors appear to be important in controlling relative Pt−P bond strengths. The Pt−S bonds in 11 and Pt(dppe)(Me)(SPh) are stronger than the analogous Pt−P bonds in 1 and 3. Complexes 1 and 5·THF were structurally characterized by X-ray crystallography.</abstract><pub>American Chemical Society</pub><doi>10.1021/om9708891</doi><tpages>9</tpages></addata></record> |
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title | Terminal Platinum(II) Phosphido Complexes: Synthesis, Structure, and Thermochemistry |
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