Triketiminate bis(borohydride) complexes of rare-earth metals [(2,6-Me2C6H3N=CMe)2C(2,6-Me2C6H3N=CBut)]Ln(BH4)2(THF)2 (Ln = Y, Nd): synthesis, structure, and catalytic activity in polymerization of rac-lactide, ε-caprolactone, and isoprene
A new triketimine (2,6-Me 2 C 6 H 3 N=CMe) 2 CH(2,6-Me 2 C 6 H 3 N=CBu t ) ( 1 ) was synthesized by the reaction of imidoyl chloride 2,6-Me 2 C 6 H 3 N=CClBu t with lithium diketiminate (2,6-Me 2 C 6 H 3 N=CMe) 2 CHLi. In the crystalline state, compound 1 exists in the diimineenamine form; in soluti...
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| Veröffentlicht in: | Russian chemical bulletin 2017-09, Vol.66 (9), p.1665-1674 |
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| creator | Skvortsov, G. G. Cherkasov, A. V. Trifonov, A. A. |
| description | A new triketimine (2,6-Me
2
C
6
H
3
N=CMe)
2
CH(2,6-Me
2
C
6
H
3
N=CBu
t
) (
1
) was synthesized by the reaction of imidoyl chloride 2,6-Me
2
C
6
H
3
N=CClBu
t
with lithium diketiminate (2,6-Me
2
C
6
H
3
N=CMe)
2
CHLi. In the crystalline state, compound
1
exists in the diimineenamine form; in solution, in the triimine form. The metalation of triketimine
1
with
n
-butyllithium in THF at 0 °C produced lithium triketiminate [(2,6-Me
2
C
6
H
3
N=CMe)
2
C(2,6-Me
2
C
6
H
3
N=CBu
t
)]Li(THF)
2
(
2
). The metathesis reactions of Ln(BH
4
)
3
(THF)
3
(Ln = Y, Nd) with compound
2
(1: 1 molar ratio, THF) gave the neutral triketiminate bis(borohydride) complexes [(2,6-Me
2
C
6
H
3
N=CMe)
2
C(2,6-Me
2
C
6
H
3
N=CBu
t
)]Ln(BH
4
)
2
(THF)
2
(Ln = Y (
3
), Nd (
4
)). As opposed to the complexes with neutral triketimine, the monoanionic triketiminate ligand is coordinated to Li and Y or Nd cations in a bidentate fashion. Complexes
3
and
4
catalyze the polymerization of
rac
-lactide and ε-caprolactone; in combination with [Ph
3
C][B(C
6
F
5
)
4
] and AlBu
3
i
(1 : 1 : 10 molar ratio), these compounds exhibit catalytic activity in the polymerization of isoprene. |
| doi_str_mv | 10.1007/s11172-017-1939-9 |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_journals_1981173644</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>1981173644</sourcerecordid><originalsourceid>FETCH-LOGICAL-c2319-1fe57af33251c26e086e7f95b773f452168481043ff12d1cab70d563e2e6b40d3</originalsourceid><addsrcrecordid>eNp1kc2K1EAUhYMoOI4-gLsCNwl0af0kqUSYhRMcW-gZN-1CREKlcmPX2KmKVRUxvpev4bP4CFaTWYjg6l4u55x74EuSp5Q8p4SIF55SKhgmVGBa8xrX95IzWgiOayro_biTssQFq4qHySPvbwkhrKqqs-T33ukvEPSojQyAOu3Tzjp7WHqne8iQsuN0hO_gkR2Qkw4wSBcOaIQgjx59TNmmxNfAmnLLby6aa8hY88_tcg7Zp51JL7d5xtL99ipjKN0ZdIE-bNBNn71EfjHhAF77DfLBzSrMDjZImh4pGd8sQSskVdDfdFiQNmiyx2UEp3_IoK1Zmyl8PEn6aPz1Eys5OXs6WHOXpL2dHBh4nDwYYnN4cjfPk_dXr_fNFu_evXnbvNphxTitMR2gEHLgnBVUsRJIVYIY6qITgg95wWhZ5RUlOR8GynqqZCdIX5QcGJRdTnp-njxbc2ORrzP40N7a2Zn4sqV1FWHxMs-jiq4q5az3DoZ2cnqUbmkpaU9g2xVsG8G2J7BtHT1s9fioNZ_B_ZX8X9MfShKkSQ</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>1981173644</pqid></control><display><type>article</type><title>Triketiminate bis(borohydride) complexes of rare-earth metals [(2,6-Me2C6H3N=CMe)2C(2,6-Me2C6H3N=CBut)]Ln(BH4)2(THF)2 (Ln = Y, Nd): synthesis, structure, and catalytic activity in polymerization of rac-lactide, ε-caprolactone, and isoprene</title><source>SpringerLink Journals</source><creator>Skvortsov, G. G. ; Cherkasov, A. V. ; Trifonov, A. A.</creator><creatorcontrib>Skvortsov, G. G. ; Cherkasov, A. V. ; Trifonov, A. A.</creatorcontrib><description>A new triketimine (2,6-Me
2
C
6
H
3
N=CMe)
2
CH(2,6-Me
2
C
6
H
3
N=CBu
t
) (
1
) was synthesized by the reaction of imidoyl chloride 2,6-Me
2
C
6
H
3
N=CClBu
t
with lithium diketiminate (2,6-Me
2
C
6
H
3
N=CMe)
2
CHLi. In the crystalline state, compound
1
exists in the diimineenamine form; in solution, in the triimine form. The metalation of triketimine
1
with
n
-butyllithium in THF at 0 °C produced lithium triketiminate [(2,6-Me
2
C
6
H
3
N=CMe)
2
C(2,6-Me
2
C
6
H
3
N=CBu
t
)]Li(THF)
2
(
2
). The metathesis reactions of Ln(BH
4
)
3
(THF)
3
(Ln = Y, Nd) with compound
2
(1: 1 molar ratio, THF) gave the neutral triketiminate bis(borohydride) complexes [(2,6-Me
2
C
6
H
3
N=CMe)
2
C(2,6-Me
2
C
6
H
3
N=CBu
t
)]Ln(BH
4
)
2
(THF)
2
(Ln = Y (
3
), Nd (
4
)). As opposed to the complexes with neutral triketimine, the monoanionic triketiminate ligand is coordinated to Li and Y or Nd cations in a bidentate fashion. Complexes
3
and
4
catalyze the polymerization of
rac
-lactide and ε-caprolactone; in combination with [Ph
3
C][B(C
6
F
5
)
4
] and AlBu
3
i
(1 : 1 : 10 molar ratio), these compounds exhibit catalytic activity in the polymerization of isoprene.</description><identifier>ISSN: 1066-5285</identifier><identifier>EISSN: 1573-9171</identifier><identifier>DOI: 10.1007/s11172-017-1939-9</identifier><language>eng</language><publisher>New York: Springer US</publisher><subject>Butyllithium ; Catalysis ; Catalytic activity ; Chemical synthesis ; Chemistry ; Chemistry and Materials Science ; Chemistry/Food Science ; Coordination compounds ; Full Articles ; Inorganic Chemistry ; Isoprene ; Lithium ; Metathesis ; Organic Chemistry ; Polymerization ; Rare earth elements</subject><ispartof>Russian chemical bulletin, 2017-09, Vol.66 (9), p.1665-1674</ispartof><rights>Springer Science+Business Media, LLC, part of Springer Nature 2017</rights><rights>Copyright Springer Science & Business Media 2017</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c2319-1fe57af33251c26e086e7f95b773f452168481043ff12d1cab70d563e2e6b40d3</citedby><cites>FETCH-LOGICAL-c2319-1fe57af33251c26e086e7f95b773f452168481043ff12d1cab70d563e2e6b40d3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://link.springer.com/content/pdf/10.1007/s11172-017-1939-9$$EPDF$$P50$$Gspringer$$H</linktopdf><linktohtml>$$Uhttps://link.springer.com/10.1007/s11172-017-1939-9$$EHTML$$P50$$Gspringer$$H</linktohtml><link.rule.ids>314,776,780,27901,27902,41464,42533,51294</link.rule.ids></links><search><creatorcontrib>Skvortsov, G. G.</creatorcontrib><creatorcontrib>Cherkasov, A. V.</creatorcontrib><creatorcontrib>Trifonov, A. A.</creatorcontrib><title>Triketiminate bis(borohydride) complexes of rare-earth metals [(2,6-Me2C6H3N=CMe)2C(2,6-Me2C6H3N=CBut)]Ln(BH4)2(THF)2 (Ln = Y, Nd): synthesis, structure, and catalytic activity in polymerization of rac-lactide, ε-caprolactone, and isoprene</title><title>Russian chemical bulletin</title><addtitle>Russ Chem Bull</addtitle><description>A new triketimine (2,6-Me
2
C
6
H
3
N=CMe)
2
CH(2,6-Me
2
C
6
H
3
N=CBu
t
) (
1
) was synthesized by the reaction of imidoyl chloride 2,6-Me
2
C
6
H
3
N=CClBu
t
with lithium diketiminate (2,6-Me
2
C
6
H
3
N=CMe)
2
CHLi. In the crystalline state, compound
1
exists in the diimineenamine form; in solution, in the triimine form. The metalation of triketimine
1
with
n
-butyllithium in THF at 0 °C produced lithium triketiminate [(2,6-Me
2
C
6
H
3
N=CMe)
2
C(2,6-Me
2
C
6
H
3
N=CBu
t
)]Li(THF)
2
(
2
). The metathesis reactions of Ln(BH
4
)
3
(THF)
3
(Ln = Y, Nd) with compound
2
(1: 1 molar ratio, THF) gave the neutral triketiminate bis(borohydride) complexes [(2,6-Me
2
C
6
H
3
N=CMe)
2
C(2,6-Me
2
C
6
H
3
N=CBu
t
)]Ln(BH
4
)
2
(THF)
2
(Ln = Y (
3
), Nd (
4
)). As opposed to the complexes with neutral triketimine, the monoanionic triketiminate ligand is coordinated to Li and Y or Nd cations in a bidentate fashion. Complexes
3
and
4
catalyze the polymerization of
rac
-lactide and ε-caprolactone; in combination with [Ph
3
C][B(C
6
F
5
)
4
] and AlBu
3
i
(1 : 1 : 10 molar ratio), these compounds exhibit catalytic activity in the polymerization of isoprene.</description><subject>Butyllithium</subject><subject>Catalysis</subject><subject>Catalytic activity</subject><subject>Chemical synthesis</subject><subject>Chemistry</subject><subject>Chemistry and Materials Science</subject><subject>Chemistry/Food Science</subject><subject>Coordination compounds</subject><subject>Full Articles</subject><subject>Inorganic Chemistry</subject><subject>Isoprene</subject><subject>Lithium</subject><subject>Metathesis</subject><subject>Organic Chemistry</subject><subject>Polymerization</subject><subject>Rare earth elements</subject><issn>1066-5285</issn><issn>1573-9171</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2017</creationdate><recordtype>article</recordtype><recordid>eNp1kc2K1EAUhYMoOI4-gLsCNwl0af0kqUSYhRMcW-gZN-1CREKlcmPX2KmKVRUxvpev4bP4CFaTWYjg6l4u55x74EuSp5Q8p4SIF55SKhgmVGBa8xrX95IzWgiOayro_biTssQFq4qHySPvbwkhrKqqs-T33ukvEPSojQyAOu3Tzjp7WHqne8iQsuN0hO_gkR2Qkw4wSBcOaIQgjx59TNmmxNfAmnLLby6aa8hY88_tcg7Zp51JL7d5xtL99ipjKN0ZdIE-bNBNn71EfjHhAF77DfLBzSrMDjZImh4pGd8sQSskVdDfdFiQNmiyx2UEp3_IoK1Zmyl8PEn6aPz1Eys5OXs6WHOXpL2dHBh4nDwYYnN4cjfPk_dXr_fNFu_evXnbvNphxTitMR2gEHLgnBVUsRJIVYIY6qITgg95wWhZ5RUlOR8GynqqZCdIX5QcGJRdTnp-njxbc2ORrzP40N7a2Zn4sqV1FWHxMs-jiq4q5az3DoZ2cnqUbmkpaU9g2xVsG8G2J7BtHT1s9fioNZ_B_ZX8X9MfShKkSQ</recordid><startdate>20170901</startdate><enddate>20170901</enddate><creator>Skvortsov, G. G.</creator><creator>Cherkasov, A. V.</creator><creator>Trifonov, A. A.</creator><general>Springer US</general><general>Springer Nature B.V</general><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>20170901</creationdate><title>Triketiminate bis(borohydride) complexes of rare-earth metals [(2,6-Me2C6H3N=CMe)2C(2,6-Me2C6H3N=CBut)]Ln(BH4)2(THF)2 (Ln = Y, Nd): synthesis, structure, and catalytic activity in polymerization of rac-lactide, ε-caprolactone, and isoprene</title><author>Skvortsov, G. G. ; Cherkasov, A. V. ; Trifonov, A. A.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c2319-1fe57af33251c26e086e7f95b773f452168481043ff12d1cab70d563e2e6b40d3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2017</creationdate><topic>Butyllithium</topic><topic>Catalysis</topic><topic>Catalytic activity</topic><topic>Chemical synthesis</topic><topic>Chemistry</topic><topic>Chemistry and Materials Science</topic><topic>Chemistry/Food Science</topic><topic>Coordination compounds</topic><topic>Full Articles</topic><topic>Inorganic Chemistry</topic><topic>Isoprene</topic><topic>Lithium</topic><topic>Metathesis</topic><topic>Organic Chemistry</topic><topic>Polymerization</topic><topic>Rare earth elements</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Skvortsov, G. G.</creatorcontrib><creatorcontrib>Cherkasov, A. V.</creatorcontrib><creatorcontrib>Trifonov, A. A.</creatorcontrib><collection>CrossRef</collection><jtitle>Russian chemical bulletin</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Skvortsov, G. G.</au><au>Cherkasov, A. V.</au><au>Trifonov, A. A.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Triketiminate bis(borohydride) complexes of rare-earth metals [(2,6-Me2C6H3N=CMe)2C(2,6-Me2C6H3N=CBut)]Ln(BH4)2(THF)2 (Ln = Y, Nd): synthesis, structure, and catalytic activity in polymerization of rac-lactide, ε-caprolactone, and isoprene</atitle><jtitle>Russian chemical bulletin</jtitle><stitle>Russ Chem Bull</stitle><date>2017-09-01</date><risdate>2017</risdate><volume>66</volume><issue>9</issue><spage>1665</spage><epage>1674</epage><pages>1665-1674</pages><issn>1066-5285</issn><eissn>1573-9171</eissn><abstract>A new triketimine (2,6-Me
2
C
6
H
3
N=CMe)
2
CH(2,6-Me
2
C
6
H
3
N=CBu
t
) (
1
) was synthesized by the reaction of imidoyl chloride 2,6-Me
2
C
6
H
3
N=CClBu
t
with lithium diketiminate (2,6-Me
2
C
6
H
3
N=CMe)
2
CHLi. In the crystalline state, compound
1
exists in the diimineenamine form; in solution, in the triimine form. The metalation of triketimine
1
with
n
-butyllithium in THF at 0 °C produced lithium triketiminate [(2,6-Me
2
C
6
H
3
N=CMe)
2
C(2,6-Me
2
C
6
H
3
N=CBu
t
)]Li(THF)
2
(
2
). The metathesis reactions of Ln(BH
4
)
3
(THF)
3
(Ln = Y, Nd) with compound
2
(1: 1 molar ratio, THF) gave the neutral triketiminate bis(borohydride) complexes [(2,6-Me
2
C
6
H
3
N=CMe)
2
C(2,6-Me
2
C
6
H
3
N=CBu
t
)]Ln(BH
4
)
2
(THF)
2
(Ln = Y (
3
), Nd (
4
)). As opposed to the complexes with neutral triketimine, the monoanionic triketiminate ligand is coordinated to Li and Y or Nd cations in a bidentate fashion. Complexes
3
and
4
catalyze the polymerization of
rac
-lactide and ε-caprolactone; in combination with [Ph
3
C][B(C
6
F
5
)
4
] and AlBu
3
i
(1 : 1 : 10 molar ratio), these compounds exhibit catalytic activity in the polymerization of isoprene.</abstract><cop>New York</cop><pub>Springer US</pub><doi>10.1007/s11172-017-1939-9</doi><tpages>10</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1066-5285 |
| ispartof | Russian chemical bulletin, 2017-09, Vol.66 (9), p.1665-1674 |
| issn | 1066-5285 1573-9171 |
| language | eng |
| recordid | cdi_proquest_journals_1981173644 |
| source | SpringerLink Journals |
| subjects | Butyllithium Catalysis Catalytic activity Chemical synthesis Chemistry Chemistry and Materials Science Chemistry/Food Science Coordination compounds Full Articles Inorganic Chemistry Isoprene Lithium Metathesis Organic Chemistry Polymerization Rare earth elements |
| title | Triketiminate bis(borohydride) complexes of rare-earth metals [(2,6-Me2C6H3N=CMe)2C(2,6-Me2C6H3N=CBut)]Ln(BH4)2(THF)2 (Ln = Y, Nd): synthesis, structure, and catalytic activity in polymerization of rac-lactide, ε-caprolactone, and isoprene |
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