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Reactions of heteroallenes with cyclam-based Zr(iv) complexesElectronic supplementary information (ESI) available: Tables with atomic coordinates for all optimized species and a more detailed discussion of the molecular structures of 5, 11, 16 and 18 are presented. CCDC 1010648-1010651. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4dt02851a
This work describes reactions of heteroallenes with diamido-diamine cyclam-based Zr( iv ) complexes of the general formula (Bn 2 Cyclam)ZrX 2 (X = O t Bu, 1 , O i Pr, 2 , SPh, 3 , NH t Bu, 14 ) as well as the di-orthometallated species ((C 6 H 4 CH 2 ) 2 Cyclam)Zr, 17 . The reactions of isocyanates...
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| creator | Alves, Luis G Madeira, Filipe Munhá, Rui F Barroso, Sónia Veiros, Luis F Martins, Ana M |
| description | This work describes reactions of heteroallenes with diamido-diamine cyclam-based Zr(
iv
) complexes of the general formula (Bn
2
Cyclam)ZrX
2
(X = O
t
Bu,
1
, O
i
Pr,
2
, SPh,
3
, NH
t
Bu,
14
) as well as the di-orthometallated species ((C
6
H
4
CH
2
)
2
Cyclam)Zr,
17
. The reactions of isocyanates or isothiocyanates with
1
,
2
or
3
resulted in the formation of N-bonded ureate or thioureate cyclam complexes upon [2 + 2] cycloaddition of the Zr-N
amido
bonds of the cyclam to the heteroallene (
4-9
). DFT calculations showed that κ
2
-
N
,
N
′-ureate bonding is favoured over κ
2
-
N
,
O
-ureates, which in turn may be formed in reactions with bulky isocyanates as 1-naphthyl isocyanate (NpN&z.dbd;C&z.dbd;O). The reactions of
2
with
N
,
N
′-cyclohexylcarbodiimide (CyN&z.dbd;C&z.dbd;NCy) and carbon disulfide afforded guanidinate and dithiocarbamate fragments, respectively, appended to one of the nitrogen atoms of the cyclam ligand. These reactions represent a reliable method for the synthesis of asymmetrically N-functionalized cyclams giving rise to
C
1
symmetry Zr(
iv
) species by addition of one equivalent of heteroallenes. The reaction of (Bn
2
Cyclam)Zr(NH
t
Bu)
2
,
14
, with one equivalent of mesityl isocyanate (MesN&z.dbd;C&z.dbd;O) also proceeds through insertion, involving one Zr-NH
t
Bu bond. However, it was observed that the reaction of (Bn
2
Cyclam)Zr(NH
t
Bu)
2
,
14
, with MesN&z.dbd;C&z.dbd;O follows a different path if the reaction is carried out at 60 °C. In this case the reaction leads to [2 + 2] addition of the Zr-N
cyclam
bond to the isocyanate, with a concomitant occurrence of orthometallation of the one benzyl pending group of the cyclam ring. The reaction of
t
BuN&z.dbd;C&z.dbd;O with the di-orthometallated complex ((C
6
H
4
CH
2
)
2
Cyclam)Zr,
17
, also gave a κ
2
-
N
,
N
′-ureate fragment, by isocyanate addition to the macrocycle. DFT calculations on these systems were conducted in an attempt to rationalise the reactivity patterns observed.
Reactions of heteroallenes with cyclam-based Zr(
iv
) complexes are described. The products obtained revealed the formation of ureate, thioureate, guanidinate or dithiocarbamate cyclam derivatives upon [2 + 2] cycloaddition of the Zr-N
amido
bonds of the cyclam. DFT calculations clarified the reactivity patterns observed. |
| doi_str_mv | 10.1039/c4dt02851a |
| format | article |
| fullrecord | <record><control><sourceid>rsc</sourceid><recordid>TN_cdi_rsc_primary_c4dt02851a</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>c4dt02851a</sourcerecordid><originalsourceid>FETCH-rsc_primary_c4dt02851a3</originalsourceid><addsrcrecordid>eNqFUU1PAjEQXY0mInrxbjLeIBHcLt9cF4icTJSTFzK0g9R0t5u2i-LFv-6ARA4memimmTfz5r2ZKLoScVPErcGdbKsQJ_2OwOOoItq9XmOQtNonP_-kexade_8ax0kSd5LK0ecjoQza5h7sElYUyFk0hnLy8KbDCuRGGswaC_Sk4NnV9LoO0maFoXfyY0MyOJtrCb4sOJdRHtBtQOdL6zLcEkNt_DStA65RG1wYGsJsG_b0GGzG3dJap3SOgfPcCSwBbBF0pj94rC9IakYwV4CQWUegKDAfY0p7WXq_HcQGwooYZ1WlQQc-uFKG0tHOXOcWhODX3fGIPiDzFAyyZlJNSNNRCiIWcbfdb-xiRzRhwmrYwK5Huo0PLM2-OCxWLFthQPYK6XQCXGd5vAM6LOV7CeCJYPQwHcLvM11Ep0s0ni73sRpdT8az9L7hvJwXTme8zfmhvFWNbv7C54Vatv7j-ALuFLKl</addsrcrecordid><sourcetype>Enrichment Source</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Reactions of heteroallenes with cyclam-based Zr(iv) complexesElectronic supplementary information (ESI) available: Tables with atomic coordinates for all optimized species and a more detailed discussion of the molecular structures of 5, 11, 16 and 18 are presented. CCDC 1010648-1010651. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4dt02851a</title><source>Royal Society of Chemistry:Jisc Collections:Royal Society of Chemistry Read and Publish 2022-2024 (reading list)</source><creator>Alves, Luis G ; Madeira, Filipe ; Munhá, Rui F ; Barroso, Sónia ; Veiros, Luis F ; Martins, Ana M</creator><creatorcontrib>Alves, Luis G ; Madeira, Filipe ; Munhá, Rui F ; Barroso, Sónia ; Veiros, Luis F ; Martins, Ana M</creatorcontrib><description><![CDATA[This work describes reactions of heteroallenes with diamido-diamine cyclam-based Zr(
iv
) complexes of the general formula (Bn
2
Cyclam)ZrX
2
(X = O
t
Bu,
1
, O
i
Pr,
2
, SPh,
3
, NH
t
Bu,
14
) as well as the di-orthometallated species ((C
6
H
4
CH
2
)
2
Cyclam)Zr,
17
. The reactions of isocyanates or isothiocyanates with
1
,
2
or
3
resulted in the formation of N-bonded ureate or thioureate cyclam complexes upon [2 + 2] cycloaddition of the Zr-N
amido
bonds of the cyclam to the heteroallene (
4-9
). DFT calculations showed that κ
2
-
N
,
N
′-ureate bonding is favoured over κ
2
-
N
,
O
-ureates, which in turn may be formed in reactions with bulky isocyanates as 1-naphthyl isocyanate (NpN&z.dbd;C&z.dbd;O). The reactions of
2
with
N
,
N
′-cyclohexylcarbodiimide (CyN&z.dbd;C&z.dbd;NCy) and carbon disulfide afforded guanidinate and dithiocarbamate fragments, respectively, appended to one of the nitrogen atoms of the cyclam ligand. These reactions represent a reliable method for the synthesis of asymmetrically N-functionalized cyclams giving rise to
C
1
symmetry Zr(
iv
) species by addition of one equivalent of heteroallenes. The reaction of (Bn
2
Cyclam)Zr(NH
t
Bu)
2
,
14
, with one equivalent of mesityl isocyanate (MesN&z.dbd;C&z.dbd;O) also proceeds through insertion, involving one Zr-NH
t
Bu bond. However, it was observed that the reaction of (Bn
2
Cyclam)Zr(NH
t
Bu)
2
,
14
, with MesN&z.dbd;C&z.dbd;O follows a different path if the reaction is carried out at 60 °C. In this case the reaction leads to [2 + 2] addition of the Zr-N
cyclam
bond to the isocyanate, with a concomitant occurrence of orthometallation of the one benzyl pending group of the cyclam ring. The reaction of
t
BuN&z.dbd;C&z.dbd;O with the di-orthometallated complex ((C
6
H
4
CH
2
)
2
Cyclam)Zr,
17
, also gave a κ
2
-
N
,
N
′-ureate fragment, by isocyanate addition to the macrocycle. DFT calculations on these systems were conducted in an attempt to rationalise the reactivity patterns observed.
Reactions of heteroallenes with cyclam-based Zr(
iv
) complexes are described. The products obtained revealed the formation of ureate, thioureate, guanidinate or dithiocarbamate cyclam derivatives upon [2 + 2] cycloaddition of the Zr-N
amido
bonds of the cyclam. DFT calculations clarified the reactivity patterns observed.]]></description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/c4dt02851a</identifier><language>eng</language><creationdate>2014-12</creationdate><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>315,783,787,27938,27939</link.rule.ids></links><search><creatorcontrib>Alves, Luis G</creatorcontrib><creatorcontrib>Madeira, Filipe</creatorcontrib><creatorcontrib>Munhá, Rui F</creatorcontrib><creatorcontrib>Barroso, Sónia</creatorcontrib><creatorcontrib>Veiros, Luis F</creatorcontrib><creatorcontrib>Martins, Ana M</creatorcontrib><title>Reactions of heteroallenes with cyclam-based Zr(iv) complexesElectronic supplementary information (ESI) available: Tables with atomic coordinates for all optimized species and a more detailed discussion of the molecular structures of 5, 11, 16 and 18 are presented. CCDC 1010648-1010651. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4dt02851a</title><description><![CDATA[This work describes reactions of heteroallenes with diamido-diamine cyclam-based Zr(
iv
) complexes of the general formula (Bn
2
Cyclam)ZrX
2
(X = O
t
Bu,
1
, O
i
Pr,
2
, SPh,
3
, NH
t
Bu,
14
) as well as the di-orthometallated species ((C
6
H
4
CH
2
)
2
Cyclam)Zr,
17
. The reactions of isocyanates or isothiocyanates with
1
,
2
or
3
resulted in the formation of N-bonded ureate or thioureate cyclam complexes upon [2 + 2] cycloaddition of the Zr-N
amido
bonds of the cyclam to the heteroallene (
4-9
). DFT calculations showed that κ
2
-
N
,
N
′-ureate bonding is favoured over κ
2
-
N
,
O
-ureates, which in turn may be formed in reactions with bulky isocyanates as 1-naphthyl isocyanate (NpN&z.dbd;C&z.dbd;O). The reactions of
2
with
N
,
N
′-cyclohexylcarbodiimide (CyN&z.dbd;C&z.dbd;NCy) and carbon disulfide afforded guanidinate and dithiocarbamate fragments, respectively, appended to one of the nitrogen atoms of the cyclam ligand. These reactions represent a reliable method for the synthesis of asymmetrically N-functionalized cyclams giving rise to
C
1
symmetry Zr(
iv
) species by addition of one equivalent of heteroallenes. The reaction of (Bn
2
Cyclam)Zr(NH
t
Bu)
2
,
14
, with one equivalent of mesityl isocyanate (MesN&z.dbd;C&z.dbd;O) also proceeds through insertion, involving one Zr-NH
t
Bu bond. However, it was observed that the reaction of (Bn
2
Cyclam)Zr(NH
t
Bu)
2
,
14
, with MesN&z.dbd;C&z.dbd;O follows a different path if the reaction is carried out at 60 °C. In this case the reaction leads to [2 + 2] addition of the Zr-N
cyclam
bond to the isocyanate, with a concomitant occurrence of orthometallation of the one benzyl pending group of the cyclam ring. The reaction of
t
BuN&z.dbd;C&z.dbd;O with the di-orthometallated complex ((C
6
H
4
CH
2
)
2
Cyclam)Zr,
17
, also gave a κ
2
-
N
,
N
′-ureate fragment, by isocyanate addition to the macrocycle. DFT calculations on these systems were conducted in an attempt to rationalise the reactivity patterns observed.
Reactions of heteroallenes with cyclam-based Zr(
iv
) complexes are described. The products obtained revealed the formation of ureate, thioureate, guanidinate or dithiocarbamate cyclam derivatives upon [2 + 2] cycloaddition of the Zr-N
amido
bonds of the cyclam. DFT calculations clarified the reactivity patterns observed.]]></description><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2014</creationdate><recordtype>article</recordtype><sourceid/><recordid>eNqFUU1PAjEQXY0mInrxbjLeIBHcLt9cF4icTJSTFzK0g9R0t5u2i-LFv-6ARA4memimmTfz5r2ZKLoScVPErcGdbKsQJ_2OwOOoItq9XmOQtNonP_-kexade_8ax0kSd5LK0ecjoQza5h7sElYUyFk0hnLy8KbDCuRGGswaC_Sk4NnV9LoO0maFoXfyY0MyOJtrCb4sOJdRHtBtQOdL6zLcEkNt_DStA65RG1wYGsJsG_b0GGzG3dJap3SOgfPcCSwBbBF0pj94rC9IakYwV4CQWUegKDAfY0p7WXq_HcQGwooYZ1WlQQc-uFKG0tHOXOcWhODX3fGIPiDzFAyyZlJNSNNRCiIWcbfdb-xiRzRhwmrYwK5Huo0PLM2-OCxWLFthQPYK6XQCXGd5vAM6LOV7CeCJYPQwHcLvM11Ep0s0ni73sRpdT8az9L7hvJwXTme8zfmhvFWNbv7C54Vatv7j-ALuFLKl</recordid><startdate>20141216</startdate><enddate>20141216</enddate><creator>Alves, Luis G</creator><creator>Madeira, Filipe</creator><creator>Munhá, Rui F</creator><creator>Barroso, Sónia</creator><creator>Veiros, Luis F</creator><creator>Martins, Ana M</creator><scope/></search><sort><creationdate>20141216</creationdate><title>Reactions of heteroallenes with cyclam-based Zr(iv) complexesElectronic supplementary information (ESI) available: Tables with atomic coordinates for all optimized species and a more detailed discussion of the molecular structures of 5, 11, 16 and 18 are presented. CCDC 1010648-1010651. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4dt02851a</title><author>Alves, Luis G ; Madeira, Filipe ; Munhá, Rui F ; Barroso, Sónia ; Veiros, Luis F ; Martins, Ana M</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-rsc_primary_c4dt02851a3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2014</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Alves, Luis G</creatorcontrib><creatorcontrib>Madeira, Filipe</creatorcontrib><creatorcontrib>Munhá, Rui F</creatorcontrib><creatorcontrib>Barroso, Sónia</creatorcontrib><creatorcontrib>Veiros, Luis F</creatorcontrib><creatorcontrib>Martins, Ana M</creatorcontrib></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Alves, Luis G</au><au>Madeira, Filipe</au><au>Munhá, Rui F</au><au>Barroso, Sónia</au><au>Veiros, Luis F</au><au>Martins, Ana M</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Reactions of heteroallenes with cyclam-based Zr(iv) complexesElectronic supplementary information (ESI) available: Tables with atomic coordinates for all optimized species and a more detailed discussion of the molecular structures of 5, 11, 16 and 18 are presented. CCDC 1010648-1010651. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4dt02851a</atitle><date>2014-12-16</date><risdate>2014</risdate><volume>44</volume><issue>3</issue><spage>1441</spage><epage>1455</epage><pages>1441-1455</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><notes>11</notes><notes>For ESI and crystallographic data in CIF or other electronic format see DOI</notes><notes>1010648-1010651</notes><notes>10.1039/c4dt02851a</notes><notes>5</notes><notes>16</notes><notes>are presented. CCDC</notes><notes>and</notes><notes>18</notes><notes>,</notes><notes>Electronic supplementary information (ESI) available: Tables with atomic coordinates for all optimized species and a more detailed discussion of the molecular structures of</notes><abstract><![CDATA[This work describes reactions of heteroallenes with diamido-diamine cyclam-based Zr(
iv
) complexes of the general formula (Bn
2
Cyclam)ZrX
2
(X = O
t
Bu,
1
, O
i
Pr,
2
, SPh,
3
, NH
t
Bu,
14
) as well as the di-orthometallated species ((C
6
H
4
CH
2
)
2
Cyclam)Zr,
17
. The reactions of isocyanates or isothiocyanates with
1
,
2
or
3
resulted in the formation of N-bonded ureate or thioureate cyclam complexes upon [2 + 2] cycloaddition of the Zr-N
amido
bonds of the cyclam to the heteroallene (
4-9
). DFT calculations showed that κ
2
-
N
,
N
′-ureate bonding is favoured over κ
2
-
N
,
O
-ureates, which in turn may be formed in reactions with bulky isocyanates as 1-naphthyl isocyanate (NpN&z.dbd;C&z.dbd;O). The reactions of
2
with
N
,
N
′-cyclohexylcarbodiimide (CyN&z.dbd;C&z.dbd;NCy) and carbon disulfide afforded guanidinate and dithiocarbamate fragments, respectively, appended to one of the nitrogen atoms of the cyclam ligand. These reactions represent a reliable method for the synthesis of asymmetrically N-functionalized cyclams giving rise to
C
1
symmetry Zr(
iv
) species by addition of one equivalent of heteroallenes. The reaction of (Bn
2
Cyclam)Zr(NH
t
Bu)
2
,
14
, with one equivalent of mesityl isocyanate (MesN&z.dbd;C&z.dbd;O) also proceeds through insertion, involving one Zr-NH
t
Bu bond. However, it was observed that the reaction of (Bn
2
Cyclam)Zr(NH
t
Bu)
2
,
14
, with MesN&z.dbd;C&z.dbd;O follows a different path if the reaction is carried out at 60 °C. In this case the reaction leads to [2 + 2] addition of the Zr-N
cyclam
bond to the isocyanate, with a concomitant occurrence of orthometallation of the one benzyl pending group of the cyclam ring. The reaction of
t
BuN&z.dbd;C&z.dbd;O with the di-orthometallated complex ((C
6
H
4
CH
2
)
2
Cyclam)Zr,
17
, also gave a κ
2
-
N
,
N
′-ureate fragment, by isocyanate addition to the macrocycle. DFT calculations on these systems were conducted in an attempt to rationalise the reactivity patterns observed.
Reactions of heteroallenes with cyclam-based Zr(
iv
) complexes are described. The products obtained revealed the formation of ureate, thioureate, guanidinate or dithiocarbamate cyclam derivatives upon [2 + 2] cycloaddition of the Zr-N
amido
bonds of the cyclam. DFT calculations clarified the reactivity patterns observed.]]></abstract><doi>10.1039/c4dt02851a</doi><tpages>15</tpages></addata></record> |
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| source | Royal Society of Chemistry:Jisc Collections:Royal Society of Chemistry Read and Publish 2022-2024 (reading list) |
| title | Reactions of heteroallenes with cyclam-based Zr(iv) complexesElectronic supplementary information (ESI) available: Tables with atomic coordinates for all optimized species and a more detailed discussion of the molecular structures of 5, 11, 16 and 18 are presented. CCDC 1010648-1010651. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4dt02851a |
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