- Email: [email protected]
Encapsulated copper ions: Cryptates and cascade complexes.
COPPER COORDINATION CHEMISTRY: POSTERS 55
P31
INVESTIGATION OF COPPER(I) AND COPPER COMPLEXES OF NEW PTERIN CHELATES. &4. Sarwar. Nasir. Dong-Heon Lee and Kenneth D.--Karlin, Departments of Chemistry, The --------i* Johns Hopkins University, Baitimore, MD 212 I (I UJA To effect arene hydroxylation, phenylalanine hydroxylase from Chromobacterium vioiaceum requires the reaction of 02 with copper(I) in the presence of a tetrahydropterin cofactor. In an effort to understand the structural and mechanistic aspects of the coordination and a-activation chemistry involved in this reaction, we have constructed novel new oxidized ptezin ligands and their copper complexes, and are studying their redox behavior.1 The synthesis and characterization of some new related pterin chelates and their copper complexes will be described. Attempts at generating reduced pterin complexes will he mentioned. 1. M. S. Nasir et. al., J. Am. Chem. Sot., 114, 2264 (1992).
P32
ENCAPSULATED COPPER IONS: CRYPTATES AND CASCADE COMPLEXES. Lu Q~II**~.V McKee= and m hb: a CM Dept. @teats Univmity, B&fast BT9 SAG, N. Ireland .b @en Vnivedy, B@st Bl7 ISV. N. Ir&nd .c Chmiatry Dept. University ofCanterbtq, Chriatchtwch I, New Zealand. ligands (prepared via [2+3] condensation of tris-ethylamino amine @en) The new (1) azaqptd a:,.,h-.rl.\(2) mvvl kn.t. fnv #.PI;_C .&th “&“I \u-uu.l,&a,_ U” pauu &IV-ID a”1 wy~ W_“Aaw. Dicoppf cryptates of the hexaimino ligands are air-stable, irrespective of the redox potential for +1/+2 interconvgsion, suggesting kinetic stabilkation of some of the cryptates. In most cases stable dicopper(II) complexes are not isolated, although two p-OH dicqper(H) cryptates have been obtained. In the octaamino ligand series, on the other hand, dicopper(II) cryptates are readily obtained, unbridged or incorporating one-, two-, and three-atom bridges. Significant interaction is mediated through these bridges. The interaction of dicopp@) cryptates of the octaamino ligands with 02 and CO will be reported. 1) J-M Lehn et al., J C/IWI Sot., CM. Common.. 1987, 1691 : D McDowell and J Nelson,
Tetrahedron Left., 1988 385.
P33
CUA-LIGANDSTRE’IWIING RESONANCE BAMAN BANDS OF cyToclHRoME OXIDASE BY NEAR-INFRARED
y , T.kms), S.Takahashi* LShinzawa-Itohb), S.Yoshikawab) and T.Kitagawaa) I&tWe&rMok&rScience, OkmakiNationalReseamh hadtut&), 0hzuakf444,andFaculty ofS ciknce, Himeji Institute ojTechtwlt#~,~ KiuuajcAkqpn, Hyq 678-12, Jam We have succeeded in observing resonance Raman bands assi ble to the CuA-S and Cu - stretching modes for resting ochrome oxi!!Kz upon 830 nm excitation we examinede $ ectsof Aq . Inthisstu ochromec and redox states of other centers on % e CuA-Ligand stretching% equency. No distinct frequency shift was observed upon complex formation of the oxidase with gtochrome c and redox cb e in other metal centers. 1.Takahashi et c& 1991, J. Am. 7% em. Sot., 113,~9401.
P31
INVESTIGATION OF COPPER(I) AND COPPER COMPLEXES OF NEW PTERIN CHELATES. &4. Sarwar. Nasir. Dong-Heon Lee and Kenneth D.--Karlin, Departments of Chemistry, The --------i* Johns Hopkins University, Baitimore, MD 212 I (I UJA To effect arene hydroxylation, phenylalanine hydroxylase from Chromobacterium vioiaceum requires the reaction of 02 with copper(I) in the presence of a tetrahydropterin cofactor. In an effort to understand the structural and mechanistic aspects of the coordination and a-activation chemistry involved in this reaction, we have constructed novel new oxidized ptezin ligands and their copper complexes, and are studying their redox behavior.1 The synthesis and characterization of some new related pterin chelates and their copper complexes will be described. Attempts at generating reduced pterin complexes will he mentioned. 1. M. S. Nasir et. al., J. Am. Chem. Sot., 114, 2264 (1992).
P32
ENCAPSULATED COPPER IONS: CRYPTATES AND CASCADE COMPLEXES. Lu Q~II**~.V McKee= and m hb: a CM Dept. @teats Univmity, B&fast BT9 SAG, N. Ireland .b @en Vnivedy, B@st Bl7 ISV. N. Ir&nd .c Chmiatry Dept. University ofCanterbtq, Chriatchtwch I, New Zealand. ligands (prepared via [2+3] condensation of tris-ethylamino amine @en) The new (1) azaqptd a:,.,h-.rl.\(2) mvvl kn.t. fnv #.PI;_C .&th “&“I \u-uu.l,&a,_ U” pauu &IV-ID a”1 wy~ W_“Aaw. Dicoppf cryptates of the hexaimino ligands are air-stable, irrespective of the redox potential for +1/+2 interconvgsion, suggesting kinetic stabilkation of some of the cryptates. In most cases stable dicopper(II) complexes are not isolated, although two p-OH dicqper(H) cryptates have been obtained. In the octaamino ligand series, on the other hand, dicopper(II) cryptates are readily obtained, unbridged or incorporating one-, two-, and three-atom bridges. Significant interaction is mediated through these bridges. The interaction of dicopp@) cryptates of the octaamino ligands with 02 and CO will be reported. 1) J-M Lehn et al., J C/IWI Sot., CM. Common.. 1987, 1691 : D McDowell and J Nelson,
Tetrahedron Left., 1988 385.
P33
CUA-LIGANDSTRE’IWIING RESONANCE BAMAN BANDS OF cyToclHRoME OXIDASE BY NEAR-INFRARED
y , T.kms), S.Takahashi* LShinzawa-Itohb), S.Yoshikawab) and T.Kitagawaa) I&tWe&rMok&rScience, OkmakiNationalReseamh hadtut&), 0hzuakf444,andFaculty ofS ciknce, Himeji Institute ojTechtwlt#~,~ KiuuajcAkqpn, Hyq 678-12, Jam We have succeeded in observing resonance Raman bands assi ble to the CuA-S and Cu - stretching modes for resting ochrome oxi!!Kz upon 830 nm excitation we examinede $ ectsof Aq . Inthisstu ochromec and redox states of other centers on % e CuA-Ligand stretching% equency. No distinct frequency shift was observed upon complex formation of the oxidase with gtochrome c and redox cb e in other metal centers. 1.Takahashi et c& 1991, J. Am. 7% em. Sot., 113,~9401.