首页> 外文学位 >Substitution chemistry of ruthenium clusters with the diphosphine ligands: 4,5-bis(diphenylphosphino)-4-cyclo-penten-1,3-dione (BPCD), (Z)-Ph(2)PCH=CHPPh(2) and 3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone (BMF).

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Substitution chemistry of ruthenium clusters with the diphosphine ligands: 4,5-bis(diphenylphosphino)-4-cyclo-penten-1,3-dione (BPCD), (Z)-Ph(2)PCH=CHPPh(2) and 3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone (BMF).

机译：具有二膦配体的钌簇的取代化学：4,5-双（二苯基膦基）-4-环戊烯-1,3-二酮（BPCD），（Z）-Ph（2）PCH = CHPPh（2）和3 ，4-双（二苯基膦基）-5-甲氧基-2（5H）-呋喃酮（BMF）。

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The reaction between the redox-active diphosphine ligand bpcd and Ru{dollar}sb3{dollar}(CO){dollar}sb{lcub}12{rcub}{dollar} has been examined under a variety of conditions. Thermolysis of {dollar}rm Rusb3(CO)sb{lcub}12{rcub}{dollar} with bpcd affords the binuclear compounds {dollar}rm Rusb2(CO)sb6(bpcd){dollar} (3) and {dollar}rm Rusb2(CO)sb6lbrackmu{dollar}-{dollar}rm overline{lcub}C{lcub}={rcub}C(PPhsb2)C(O)CHsb2C{rcub}(O)rbrack (musb2{dollar}-PPh{dollar}sb2){dollar} (4) as the major and minor products, respectively. The disubstituted cluster {dollar}rm Rusb3(CO)sb{lcub}10{rcub}(bpcd){dollar} (2) has been synthesized and shown to contain a chelating bpcd ligand, on the basis of IR and {dollar}sp{lcub}31{rcub}{dollar}P NMR data. The cluster 2 (chelating isomer) undergoes cluster fragmentation at ambient temperatures in the dark to give the binuclear compound 3 and {dollar}rm Rusb3(CO)sb{lcub}12{rcub},{dollar} with no evidence for the formation of 4. Both 3 and 4 have been isolated and fully characterized in solution by IR and NMR spectroscopy, and the solid-state structure of each new binuclear compound has been established by X-ray diffraction analysis. Independent experiments reveal that dinuclear 3 is converted to 4 by 366 nm light with a quantum efficiency of 0.0364.; Near-UV irradiation of 3 in the presence of 11 equivalents of PMe{dollar}sb3{dollar} gave 4 (13%), {dollar}rm Rusb2(CO)sb5(bpcd)(PMesb3){dollar}(7)(5%), and {dollar}rm Rusb2(CO)sb5lbrack mu{dollar}-{dollar}rm overline{lcub}C{lcub}={rcub}C(PPhsb2)C(O)CHsb2C{rcub}(O)rbrack(musb2{dollar}-{dollar}rm PPhsb2){dollar}-(PMe{dollar}sb3){dollar} (8) (6%). Both 7 and 8 have been isolated and fully characterized in solution by IR and NMR spectroscopy, and the solid-state structure of each new binuclear compound has been established by X-ray diffraction analysis.; Irradiation of either {dollar}rm Rusb2(CO)sb6(bpcd){dollar} or {dollar}rm Rusb2(CO)sb6lbrack{dollar}(Z)-{dollar}rm Phsb2PCH{lcub}={rcub}CHPPhsb2rbrack{dollar} in {dollar}rm CHsb2Clsb2{dollar} solution with excess dimethyl acetylenedicarboxylate at room temperature furnishes the zwitterionic (Z)-dimetallated olefin complexes {dollar}rm Rusb2(CO)sb6(bpcd)lbrackmu{dollar}-(Z)-{dollar}rm MeOsb2CC{lcub}={rcub}CCOsb2Merbrack{dollar} (11) or {dollar}rm Rusb2(CO)sb6C{dollar}(Z)-{dollar}rm Phsb2PCH{lcub}={rcub}CHPPhsb2rbracklbrackmu{dollar}-(Z)-{dollar}rm MeOsb2CC{lcub}={rcub}CCOsb2Merbrack{dollar} (12), respectively. Both 11 and 12 have been isolated and fully characterized in solution by IR and NMR spectroscopy. The solid-state structure of 11 was determined by X-ray diffraction analysis.; The acetylide-bridged cluster {dollar}rm Rusb3(CO)sb9(musb2{dollar}-H)({dollar}musb3{dollar}-{dollar}etasp2{dollar}-{dollar}rm C{lcub}equiv{rcub}CBusp{lcub}t{rcub}){dollar} reacts with bpcd in {dollar}rm CHsb2Clsb2{dollar} with added {dollar}rm Mesb3NO{dollar} to afford the bpcd-substituted cluster {dollar}rm Rusb3(CO)sb7(musb2{dollar}-H)({dollar}musb3{dollar}-{dollar}etasp2{dollar}-{dollar}rm C{lcub}equiv{rcub}Busp{lcub}t{rcub}{dollar}(bpcd) (14) as the only product. Interestingly, under the same conditions the reaction of the related phenylacetylide cluster {dollar}rm Rusb3(CO)sb9(musb2H)(musb3{dollar}-{dollar}etasp2{dollar}-{dollar}rm C{lcub}equiv{rcub}CPh){dollar} with bpcd not only affords the chelating cluster {dollar}rm Rusb3(CO)sb7(musb2{dollar}-H)({dollar}musb3{dollar}-{dollar}etasp2{dollar}-{dollar}rm C{lcub}equiv{rcub}CPh){dollar}(bpcd) (15) but also gives, as major product, the zwitterionic cluster {dollar}rm Rusb3(CO)sb7(musb2{dollar}-H) ({dollar}musb3{lcub}:{rcub}etasp2,etasp2, etasp2,etasp1,eta sp1{dollar}-PhCC(PPh{dollar}sb2)rm overline{lcub}C{lcub}={rcub}C(PPhsb 2)C(O)CHsb2C{rcub}(O)rbrack{dollar} (16), whose origin can be traced to the attack of a PPh{dollar}

机译：已经在多种条件下研究了氧化还原活性二膦配体bpcd与Ru {dollar} sb3 {dollar}（CO）{dollar} sb {lcub} 12 {rcub} {dollar}之间的反应。 {bp} rm Rusb3（CO）sb {lcub} 12 {rcub} {dollar}与bpcd的热解得到双核化合物{dol} rm Rusb2（CO）sb6（bpcd）{dollar}（3）和{dollar} rm Rusb2（CO）sb6lbrackmu {dollar}-{dollar} rm overline {lcub} C {lcub} = {rcub} C（PPhsb2）C（O）CHsb2C {rcub}（O）rbrack（musb2 {dollar} -PPh {dollar } sb2）{dollar}（4）分别作为主要产品和次要产品。根据IR和{sp}，合成了二取代簇{ruus} rm Rusb3（CO）sb {lcub} 10 {rcub}（bpcd）{dollar}（2）并显示它含有螯合的bpcd配体。 {lcub} 31 {rcub} {美元} P NMR数据。团簇2（螯合异构体）在黑暗中于环境温度下发生团簇破碎，得到双核化合物3和{dol} rm Rusb3（CO）sb {lcub} 12 {rcub}，{dollar}，没有形成4. 3和4均已分离，并通过IR和NMR光谱在溶液中充分表征，每种新的双核化合物的固态结构均已通过X射线衍射分析确定。独立实验表明，双核3被366 nm光转换为4，量子效率为0.0364。在11个当量的PMe {美元} sb3 {美元}存在下，对3进行近紫外线照射得到4（13％），{美元} rm Rusb2（CO）sb5（bpcd）（PMesb3）{美元}（7）（ 5％），并且{dol} rm Rusb2（CO）sb5lbrack mu {dollar}-{dollar} rm overline {lcub} C {lcub} = {rcub} C（PPhsb2）C（O）CHsb2C {rcub}（O） rbrack（musb2 {dollar}-{dollar} rm PPhsb2）{dollar}-（PMe {dollar} sb3）{dollar}（8）（6％）。 7和8均已通过IR和NMR光谱分离并在溶液中充分表征，每种新的双核化合物的固态结构均已通过X射线衍射分析确定。 {美元} rm Rusb2（CO）sb6（bpcd）{美元}或{美元} rm Rusb2（CO）sb6lbrack {美元}（Z）-{美元} rm Phsb2PCH {lcub} = {rcub} CHPPhsb2rbrack {dollar}的辐照}在室温下用过量的乙炔二羧酸二甲酯在{rm} rm CHsb2Clsb2 {dollar}溶液中提供两性离子（Z）-双金属化的烯烃络合物{dol} rm Rusb2（CO）sb6（bpcd）lbrackmu {dollar}-（Z）-{ dollar} rm MeOsb2CC {lcub} = {rcub} CCOsb2Merbrack {dollar}（11）或{dollar} Rusb2（CO）sb6C {dollar}（Z）-{dollar} rm Phsb2PCH {lcub} = {rcub} CHPPhsb2rbracklbrackmu {dollar }-（Z）-{美元} rm MeOsb2CC {lcub} = {rcub} CCOsb2Merbrack {美元}（12）。 11和12均已分离，并通过IR和NMR光谱在溶液中充分表征。通过X射线衍射分析确定11的固态结构。乙炔桥簇{Rusb3（CO）sb9（musb2 {dollar} -H）（{dollar} musb3 {dollar}-{dollar} etasp2 {dollar}-{dollar} rm C {lcub} equiv {rcub } CBusp {lcub} t {rcub}）{美元}与{美元} rm CHsb2Clsb2 {美元}中的bpcd反应，并添加了{美元} rm Mesb3NO {美元}，以提供被bpcd取代的簇{美元} rm Rusb3（CO） sb7（musb2 {dollar} -H）（{dollar} musb3 {dollar}-{dollar} etasp2 {dollar}-{dollar} rm C {lcub} equiv {rcub} Busp {lcub} t {rcub} {dollar}（ bpcd）（14）作为唯一产品。有趣的是，在相同条件下，相关苯乙酰胺簇{dol} rm Rusb3（CO）sb9（musb2H）（musb3 {dollar}-{dollar} etasp2 {dollar}-{具有bpcd的dollar} rm C {lcub} equiv {rcub} CPh）{dollar}不仅提供了螯合簇{dollar} rm Rusb3（CO）sb7（musb2 {dollar} -H）（{dollar} musb3 {dollar}- {dollar} etasp2 {dollar}-{dollar} rm C {lcub} equiv {rcub} CPh）{dollar}（bpcd）（15），但也提供两性离子簇{dollar} rm Rusb3（CO）作为主要产品sb7（musb2 {dollar} -H）（{dollar} musb3 {lcub}：{rcub} etasp2，e tasp2，etasp2，etasp1，eta sp1 {美元} -PhCC（PPh {美元} sb2）rm上线{lcub} C {lcub} = {rcub} C（PPhsb 2）C（O）CHsb2C {rcub}（O）rbrack {dollar}（16），其起源可以追溯到PPh的袭击{dollar}

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作者
Shen, Huanfeng.;
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作者单位

University of North Texas.;

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授予单位 University of North Texas.;
学科 Chemistry Organic.; Chemistry Inorganic.
学位 Ph.D.
年度 1997
页码 169 p.
总页数 169
原文格式 PDF
正文语种 eng
中图分类有机化学;无机化学;
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Substitution chemistry of ruthenium clusters with the diphosphine ligands: 4,5-bis(diphenylphosphino)-4-cyclo-penten-1,3-dione (BPCD), (Z)-Ph(2)PCH=CHPPh(2) and 3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone (BMF).

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