Substitution and derivatization reactions of a water soluble iron(II) complex containing a self-assembled tetradentate phosphine ligand

Andrew D Burrows; Deborah Dodds; Andrew S Kirk; John P Lowe; Mary F Mahon; John E Warren; Michael K Whittlesey

Substitution and derivatization reactions of a water soluble iron(II) complex containing a self-assembled tetradentate phosphine ligand

Andrew D Burrows, Deborah Dodds, Andrew S Kirk, John P Lowe, Mary F Mahon, John E Warren, Michael K Whittlesey

Department of Chemistry

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

15 Citations (SciVal)

Abstract

Facile substitution reactions of the two H2O ligands in the hydrophilic tetradentate phosphine complex cis-[Fe{(HOCH2)P{CH2N(CH2P(CH2OH)2)CH2}2P(CH2OH)}(H2O)2](SO4) ([Fe(L1)(H2O)2](SO4), 1) take place upon addn. of Cl-, NCS-, N3-, CO32- and CO to give [Fe(L1)X2] (2, X = Cl; 4, X = NCS; 5, X:N3), [Fe(L1)(k2-O2CO)] (6), and [Fe(L1)(CO)2](SO4) (7). The unsym. mono-substituted intermediates [Fe(L1)(H2O)(CO)](SO4) (8) and [Fe(L1)(CO)(k1-OSO3)] (9) were identified spectroscopically en-route to 7. Treatment of 1 with acetic anhydride affords the acylated deriv. [Fe{(AcOCH2)P{CH2N(CH2P(CH2OAc)2)CH2}2P(CH2OAc)}(k2-O2SO2)] ([Fe(L2)(k2-O2SO2)], 10), which has increased soly. over 1 in both org. solvents and H2O. Treatment of 1 with glycine does not lead to functionalization of L1, but substitution of the aqua ligands occurs to form [Fe(L1)(NH2CH2CO2-k2N,O)](HSO4) (11). Compd. 10 reacts with chloride to form [Fe(L2)Cl2] (12), and 12 reacts with CO in the presence of NaBPh4 to form [Fe(L2)Cl(CO)](BPh4) (13b). Both of the chlorides in 12 are substituted on reaction with NCS- and N3- to form [Fe(L2)(NCS)2] (14) and [Fe(L2)(N3)2] (15), resp. Complexes 2.H2O, 4.2H2O, 5.0.812H2O, 6.1.7H2O, 7.H2O, 10.1.3CH3C(O)CH3, 12 and 15.0.5H2O have all been crystallog. characterized.

Original language	English
Pages (from-to)	570-580
Number of pages	11
Journal	Dalton Transactions
Issue number	5
Publication status	Published - 2007

Keywords

pseudohalide
crystal structure iron hydroxymethylphosphinomethyl diazadiphosphacyclooctane halide pseudohalide glycinato carbonyl
N'-bis[bis(hydroxymethyl)phosphinomethyl]diazadiphosphacyclooctane complexes with halide
iron aqua hydroxymethylphosphinomethyl diazadiphosphacyclooctane hydrophilic coordinative substitution
Crystal structure
glycine
N'-bis[bis(hydroxymethyl)phosphinomethyl]diazadiphosphacyclooctane aqua complex with halide
Substitution reaction (of iron(II) N
and carbonyl)
and carbonyl ligands and O-acetylated deriv.)
Molecular structure (of iron(II) N

Cite this

@article{b8804d5b5c8444af9cd5abc0d5641e3d,

title = "Substitution and derivatization reactions of a water soluble iron(II) complex containing a self-assembled tetradentate phosphine ligand",

abstract = "Facile substitution reactions of the two H2O ligands in the hydrophilic tetradentate phosphine complex cis-[Fe{(HOCH2)P{CH2N(CH2P(CH2OH)2)CH2}2P(CH2OH)}(H2O)2](SO4) ([Fe(L1)(H2O)2](SO4), 1) take place upon addn. of Cl-, NCS-, N3-, CO32- and CO to give [Fe(L1)X2] (2, X = Cl; 4, X = NCS; 5, X:N3), [Fe(L1)(k2-O2CO)] (6), and [Fe(L1)(CO)2](SO4) (7). The unsym. mono-substituted intermediates [Fe(L1)(H2O)(CO)](SO4) (8) and [Fe(L1)(CO)(k1-OSO3)] (9) were identified spectroscopically en-route to 7. Treatment of 1 with acetic anhydride affords the acylated deriv. [Fe{(AcOCH2)P{CH2N(CH2P(CH2OAc)2)CH2}2P(CH2OAc)}(k2-O2SO2)] ([Fe(L2)(k2-O2SO2)], 10), which has increased soly. over 1 in both org. solvents and H2O. Treatment of 1 with glycine does not lead to functionalization of L1, but substitution of the aqua ligands occurs to form [Fe(L1)(NH2CH2CO2-k2N,O)](HSO4) (11). Compd. 10 reacts with chloride to form [Fe(L2)Cl2] (12), and 12 reacts with CO in the presence of NaBPh4 to form [Fe(L2)Cl(CO)](BPh4) (13b). Both of the chlorides in 12 are substituted on reaction with NCS- and N3- to form [Fe(L2)(NCS)2] (14) and [Fe(L2)(N3)2] (15), resp. Complexes 2.H2O, 4.2H2O, 5.0.812H2O, 6.1.7H2O, 7.H2O, 10.1.3CH3C(O)CH3, 12 and 15.0.5H2O have all been crystallog. characterized.",

keywords = "pseudohalide, crystal structure iron hydroxymethylphosphinomethyl diazadiphosphacyclooctane halide pseudohalide glycinato carbonyl, N'-bis[bis(hydroxymethyl)phosphinomethyl]diazadiphosphacyclooctane complexes with halide, iron aqua hydroxymethylphosphinomethyl diazadiphosphacyclooctane hydrophilic coordinative substitution, Crystal structure, glycine, N'-bis[bis(hydroxymethyl)phosphinomethyl]diazadiphosphacyclooctane aqua complex with halide, Substitution reaction (of iron(II) N, and carbonyl), and carbonyl ligands and O-acetylated deriv.), Molecular structure (of iron(II) N",

author = "Burrows, {Andrew D} and Deborah Dodds and Kirk, {Andrew S} and Lowe, {John P} and Mahon, {Mary F} and Warren, {John E} and Whittlesey, {Michael K}",

year = "2007",

language = "English",

pages = "570--580",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "5",

}

TY - JOUR

T1 - Substitution and derivatization reactions of a water soluble iron(II) complex containing a self-assembled tetradentate phosphine ligand

AU - Burrows, Andrew D

AU - Dodds, Deborah

AU - Kirk, Andrew S

AU - Lowe, John P

AU - Mahon, Mary F

AU - Warren, John E

AU - Whittlesey, Michael K

PY - 2007

Y1 - 2007

N2 - Facile substitution reactions of the two H2O ligands in the hydrophilic tetradentate phosphine complex cis-[Fe{(HOCH2)P{CH2N(CH2P(CH2OH)2)CH2}2P(CH2OH)}(H2O)2](SO4) ([Fe(L1)(H2O)2](SO4), 1) take place upon addn. of Cl-, NCS-, N3-, CO32- and CO to give [Fe(L1)X2] (2, X = Cl; 4, X = NCS; 5, X:N3), [Fe(L1)(k2-O2CO)] (6), and [Fe(L1)(CO)2](SO4) (7). The unsym. mono-substituted intermediates [Fe(L1)(H2O)(CO)](SO4) (8) and [Fe(L1)(CO)(k1-OSO3)] (9) were identified spectroscopically en-route to 7. Treatment of 1 with acetic anhydride affords the acylated deriv. [Fe{(AcOCH2)P{CH2N(CH2P(CH2OAc)2)CH2}2P(CH2OAc)}(k2-O2SO2)] ([Fe(L2)(k2-O2SO2)], 10), which has increased soly. over 1 in both org. solvents and H2O. Treatment of 1 with glycine does not lead to functionalization of L1, but substitution of the aqua ligands occurs to form [Fe(L1)(NH2CH2CO2-k2N,O)](HSO4) (11). Compd. 10 reacts with chloride to form [Fe(L2)Cl2] (12), and 12 reacts with CO in the presence of NaBPh4 to form [Fe(L2)Cl(CO)](BPh4) (13b). Both of the chlorides in 12 are substituted on reaction with NCS- and N3- to form [Fe(L2)(NCS)2] (14) and [Fe(L2)(N3)2] (15), resp. Complexes 2.H2O, 4.2H2O, 5.0.812H2O, 6.1.7H2O, 7.H2O, 10.1.3CH3C(O)CH3, 12 and 15.0.5H2O have all been crystallog. characterized.

AB - Facile substitution reactions of the two H2O ligands in the hydrophilic tetradentate phosphine complex cis-[Fe{(HOCH2)P{CH2N(CH2P(CH2OH)2)CH2}2P(CH2OH)}(H2O)2](SO4) ([Fe(L1)(H2O)2](SO4), 1) take place upon addn. of Cl-, NCS-, N3-, CO32- and CO to give [Fe(L1)X2] (2, X = Cl; 4, X = NCS; 5, X:N3), [Fe(L1)(k2-O2CO)] (6), and [Fe(L1)(CO)2](SO4) (7). The unsym. mono-substituted intermediates [Fe(L1)(H2O)(CO)](SO4) (8) and [Fe(L1)(CO)(k1-OSO3)] (9) were identified spectroscopically en-route to 7. Treatment of 1 with acetic anhydride affords the acylated deriv. [Fe{(AcOCH2)P{CH2N(CH2P(CH2OAc)2)CH2}2P(CH2OAc)}(k2-O2SO2)] ([Fe(L2)(k2-O2SO2)], 10), which has increased soly. over 1 in both org. solvents and H2O. Treatment of 1 with glycine does not lead to functionalization of L1, but substitution of the aqua ligands occurs to form [Fe(L1)(NH2CH2CO2-k2N,O)](HSO4) (11). Compd. 10 reacts with chloride to form [Fe(L2)Cl2] (12), and 12 reacts with CO in the presence of NaBPh4 to form [Fe(L2)Cl(CO)](BPh4) (13b). Both of the chlorides in 12 are substituted on reaction with NCS- and N3- to form [Fe(L2)(NCS)2] (14) and [Fe(L2)(N3)2] (15), resp. Complexes 2.H2O, 4.2H2O, 5.0.812H2O, 6.1.7H2O, 7.H2O, 10.1.3CH3C(O)CH3, 12 and 15.0.5H2O have all been crystallog. characterized.

KW - pseudohalide

KW - crystal structure iron hydroxymethylphosphinomethyl diazadiphosphacyclooctane halide pseudohalide glycinato carbonyl

KW - N'-bis[bis(hydroxymethyl)phosphinomethyl]diazadiphosphacyclooctane complexes with halide

KW - iron aqua hydroxymethylphosphinomethyl diazadiphosphacyclooctane hydrophilic coordinative substitution

KW - Crystal structure

KW - glycine

KW - N'-bis[bis(hydroxymethyl)phosphinomethyl]diazadiphosphacyclooctane aqua complex with halide

KW - Substitution reaction (of iron(II) N

KW - and carbonyl)

KW - and carbonyl ligands and O-acetylated deriv.)

KW - Molecular structure (of iron(II) N

M3 - Article

SN - 1477-9226

SP - 570

EP - 580

JO - Dalton Transactions

JF - Dalton Transactions

IS - 5

ER -

Substitution and derivatization reactions of a water soluble iron(II) complex containing a self-assembled tetradentate phosphine ligand

Abstract

Keywords

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