Dihapto carbamoyl (carboxamide) complexes of iron(II)

Stephen Anderson; Timothy E. Berridge; Anthony F. Hill; Ying Thong Ng; Andrew J.P. White; David J. Williams

doi:10.1021/om0306933

Dihapto carbamoyl (carboxamide) complexes of iron(II)

Stephen Anderson, Timothy E. Berridge, Anthony F. Hill^*, Ying Thong Ng, Andrew J.P. White, David J. Williams

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

8 Citations (Scopus)

Abstract

The carbamoyl ferrate Li[Fe{C(=O)N ⁱPr ₂}(CO) ₄] reacts in diethyl ether with Br ₂PPh ₃, I ₂PPh ₃, or I ₂ followed by triphenylphosphine to provide the complexes [Fe(η ²-OCN ⁱPr ₂)X-(CO) ₂(PPh ₃)] [X = I trans to PPh ₃ (1a); Br (1b) two isomers], each of which feature dihaptoC,O carbamoyl coordination. The reactions of 1a or 1b with AgBF ₄ in the presence of CO provide [Fe(η ²-OCN ⁱPr ₂)(CO) ₃(PPh ₃)]BF ₄ (2a·BF ₄), one carbonyl ligand of which is labile and readily replaced by I ^-, Br ^-, or PPh ₃ to provide 1a, 1b, or [Fe-{η ²-OCN ⁱPr ₂}(CO) ₂(PPh ₃) ₂]BF ₄(2b·BF ₄). The reaction of 1a with dppe leads to a separable mixture of the salt [Fe{η ²- OCN ⁱPr ₂}(CO) ₂(dppe)]I (3·I) and [Fe{η ²-OCN ⁱPr ₂}I(CO)(dppe)] (4). Successive treatment of Li[Fe{C(=O)N ⁱPr ₂}(CO) ₄] with ClSnPh ₃ and PPh ₃ provides the stannyl complex [Fe(η ²-OCN ⁱPr ₂)(SnPh ₃)(CO) ₂(PPh ₃)] (1d). Treating Id with iodine leads to Sn-Fe rather than Sn-C cleavage and formation of 1a. In all the above transformations the integrity of the dihapto carbamoyl coordination is ultimately retained. The crystal structures of 1d and 2b·PF ₆ are reported.

Original language	English
Pages (from-to)	2686-2693
Number of pages	8
Journal	Organometallics
Volume	23
Issue number	11
DOIs	https://doi.org/10.1021/om0306933
Publication status	Published - 24 May 2004

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10.1021/om0306933

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@article{03ac27b005d74d0981d3046467c18ff8,

title = "Dihapto carbamoyl (carboxamide) complexes of iron(II)",

abstract = "The carbamoyl ferrate Li[Fe{C(=O)N iPr 2}(CO) 4] reacts in diethyl ether with Br 2PPh 3, I 2PPh 3, or I 2 followed by triphenylphosphine to provide the complexes [Fe(η 2-OCN iPr 2)X-(CO) 2(PPh 3)] [X = I trans to PPh 3 (1a); Br (1b) two isomers], each of which feature dihaptoC,O carbamoyl coordination. The reactions of 1a or 1b with AgBF 4 in the presence of CO provide [Fe(η 2-OCN iPr 2)(CO) 3(PPh 3)]BF 4 (2a·BF 4), one carbonyl ligand of which is labile and readily replaced by I -, Br -, or PPh 3 to provide 1a, 1b, or [Fe-{η 2-OCN iPr 2}(CO) 2(PPh 3) 2]BF 4(2b·BF 4). The reaction of 1a with dppe leads to a separable mixture of the salt [Fe{η 2- OCN iPr 2}(CO) 2(dppe)]I (3·I) and [Fe{η 2-OCN iPr 2}I(CO)(dppe)] (4). Successive treatment of Li[Fe{C(=O)N iPr 2}(CO) 4] with ClSnPh 3 and PPh 3 provides the stannyl complex [Fe(η 2-OCN iPr 2)(SnPh 3)(CO) 2(PPh 3)] (1d). Treating Id with iodine leads to Sn-Fe rather than Sn-C cleavage and formation of 1a. In all the above transformations the integrity of the dihapto carbamoyl coordination is ultimately retained. The crystal structures of 1d and 2b·PF 6 are reported.",

author = "Stephen Anderson and Berridge, {Timothy E.} and Hill, {Anthony F.} and Ng, {Ying Thong} and White, {Andrew J.P.} and Williams, {David J.}",

year = "2004",

month = may,

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doi = "10.1021/om0306933",

language = "English",

volume = "23",

pages = "2686--2693",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "11",

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TY - JOUR

T1 - Dihapto carbamoyl (carboxamide) complexes of iron(II)

AU - Anderson, Stephen

AU - Berridge, Timothy E.

AU - Hill, Anthony F.

AU - Ng, Ying Thong

AU - White, Andrew J.P.

AU - Williams, David J.

PY - 2004/5/24

Y1 - 2004/5/24

N2 - The carbamoyl ferrate Li[Fe{C(=O)N iPr 2}(CO) 4] reacts in diethyl ether with Br 2PPh 3, I 2PPh 3, or I 2 followed by triphenylphosphine to provide the complexes [Fe(η 2-OCN iPr 2)X-(CO) 2(PPh 3)] [X = I trans to PPh 3 (1a); Br (1b) two isomers], each of which feature dihaptoC,O carbamoyl coordination. The reactions of 1a or 1b with AgBF 4 in the presence of CO provide [Fe(η 2-OCN iPr 2)(CO) 3(PPh 3)]BF 4 (2a·BF 4), one carbonyl ligand of which is labile and readily replaced by I -, Br -, or PPh 3 to provide 1a, 1b, or [Fe-{η 2-OCN iPr 2}(CO) 2(PPh 3) 2]BF 4(2b·BF 4). The reaction of 1a with dppe leads to a separable mixture of the salt [Fe{η 2- OCN iPr 2}(CO) 2(dppe)]I (3·I) and [Fe{η 2-OCN iPr 2}I(CO)(dppe)] (4). Successive treatment of Li[Fe{C(=O)N iPr 2}(CO) 4] with ClSnPh 3 and PPh 3 provides the stannyl complex [Fe(η 2-OCN iPr 2)(SnPh 3)(CO) 2(PPh 3)] (1d). Treating Id with iodine leads to Sn-Fe rather than Sn-C cleavage and formation of 1a. In all the above transformations the integrity of the dihapto carbamoyl coordination is ultimately retained. The crystal structures of 1d and 2b·PF 6 are reported.

AB - The carbamoyl ferrate Li[Fe{C(=O)N iPr 2}(CO) 4] reacts in diethyl ether with Br 2PPh 3, I 2PPh 3, or I 2 followed by triphenylphosphine to provide the complexes [Fe(η 2-OCN iPr 2)X-(CO) 2(PPh 3)] [X = I trans to PPh 3 (1a); Br (1b) two isomers], each of which feature dihaptoC,O carbamoyl coordination. The reactions of 1a or 1b with AgBF 4 in the presence of CO provide [Fe(η 2-OCN iPr 2)(CO) 3(PPh 3)]BF 4 (2a·BF 4), one carbonyl ligand of which is labile and readily replaced by I -, Br -, or PPh 3 to provide 1a, 1b, or [Fe-{η 2-OCN iPr 2}(CO) 2(PPh 3) 2]BF 4(2b·BF 4). The reaction of 1a with dppe leads to a separable mixture of the salt [Fe{η 2- OCN iPr 2}(CO) 2(dppe)]I (3·I) and [Fe{η 2-OCN iPr 2}I(CO)(dppe)] (4). Successive treatment of Li[Fe{C(=O)N iPr 2}(CO) 4] with ClSnPh 3 and PPh 3 provides the stannyl complex [Fe(η 2-OCN iPr 2)(SnPh 3)(CO) 2(PPh 3)] (1d). Treating Id with iodine leads to Sn-Fe rather than Sn-C cleavage and formation of 1a. In all the above transformations the integrity of the dihapto carbamoyl coordination is ultimately retained. The crystal structures of 1d and 2b·PF 6 are reported.

UR - http://www.scopus.com/inward/record.url?scp=2942590683&partnerID=8YFLogxK

U2 - 10.1021/om0306933

DO - 10.1021/om0306933

M3 - Article

SN - 0276-7333

VL - 23

SP - 2686

EP - 2693

JO - Organometallics

JF - Organometallics

IS - 11

ER -

Dihapto carbamoyl (carboxamide) complexes of iron(II)

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