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CHM 102

Carbocation is a___and___. Electrophile lewis acid
Leaving group tendency-Strong bases are___. strong acids are___leaving group. Poor leaving group strong
Leaving group tendency-F-,OH-,NH2-,CH3- (F-)>OH->NH2->CH3-
Leaving group tendency-RO-,PhO-,MeCOO-,CF3COO-,OH- (CF3COO-)>(MeCOO-)>PhO->OH->RO-
Leaving group tendency-CH3COO-,CH3SO3-,CF3SO3- [CF3SO3-]>(CH3SO3-)>(CH3COO-)
Leaving group tendency-N2 NH3 H2O [N2]>[H2O]>NH3
Leaving group tendency-Halogens (I-)>(Br-)>(Cl-)>(F-)
Leaving group tendency-Nosylate,brosylate,tosylate (NsO-)>(BsO-)>(TsO-)
Diazotization reaction___. RNH2->(NaNO2+HCl)R+ + N2
CR OF carbocation 1- Combination of nucleophile
CR OF carbocation Comb degree order___elimin degree order___. 1>2>3 3>2>1
CR OF carbocation Comb depends on temperature as___and elimn. as___. Inversly directly
CR OF carbocation Comb depends on nucleophilicity as___and basic strength as___. Directly Inversly
If during a reaction more than one alkene is produced then the most stable alkene is___. Zaitsev rule
C+ + Halogen ->C + E C/E ratio is in order F->Cl->Br->I-
Tert-butyl-C-C(+)(-C)-C Hoffman product is major
Rearangement produces a___and if the step is RDS or shift is stabilised by backbonding then__. More stable carbocation Better electron donor
Cyclopentane-CH2+->(rearrangement)___ Cyclohexane carbocation
Cyclopropane-CH2+->(rearrangement)___ Not rearranges
In dehydration of alcohol after formation of carbocation-at low temperature___,at high temperature___. Nucleophile attack Base attack
E1 lg__first and then___takes proton. Leaves base
E1 rate directly proportional to concentration of substrate and___. Independent of base
E1 rate is___to lg tendency. Directly proportional
E1 rate for different substrate___. Benzyl>allylic>3>2>1
E1 mechanism is favored by___. Good lg,polar solvent,poor base,poor nucleophile,high temperature
E1 C-C(-OH,-C)-C(-OH,-C)-C ->(conc H2SO4,heat)___. Pinacolon Tert butyl-C(=O)-C
Cyclopentane(OH)-Cyclopentane-E1 Decalin with bridge double bond
E1 reagents that take halogens SbCl5,AlCl3,AlBr3,AgNO3
E1 C-C-NH2(NaNO2,HCl)->___. C-C-ONO,C-C-Cl,C-C-O-C-C,major C-C-OH
Ae Classical carbocation mechanism >C=C<->(RDS)E->C-C<+->E-C-C-Nu
Ae Classical carbocation mechanism Rate is__and proportional to___. Second order electrophilicity of electrophile
Ae Alenylation of alkene C=C->(Catalytic H2SO4)___. Formation of carbocation,attack on alkene,deprotonation.
Ae Alkylation of alkene->(HF 0 C)___. Formation of carbocation,attack on alkene,rearrangement
Ae Hyrohalogenation of alkene___. Rate for different halogen___. RDS formation of carbocation,attack of nucleophile I>Br>Cl>F
Anti-Markonikoff addition___. ROOR->2RO'+HBr->ROH + Br'->formation of carbon radical
HF,HCL,HBr,HI__only shows Kharash-Peroxide effect. HBr
Rate of Ae >=< >= \= = >=< > >= > \= > =
Rate of Ae =-Ph__(para). OMe Me H CN NO2 OMe>Me>H>CN>NO2
Rate of Ae =-Ph__ OMe(meta,para),NO2(meta,para),H OMe(p)>H>OMe(m)>NO2(m)>NO2(p)
Rate of Ae Styrene and stillbene Stillbene>styrene
Ae Triple bond___react when not in conjugation, but when it is in conjugation the triple bond___. Will not is first to react
In peroxide reaction the -ve part in following reagents CCl4 CBr4 CCl3Br CBr3-Cl H-CF3 I-CF3 H-CI3 EtSH is___.
Prins reaction Alkene+___(dil. H2SO4)->___by___. HCHO 1,3 diol alkene C attack HCHO then OH attacks positive charged carbon
Non classical carbocation mechanism___ First Br attacks on double bond and then other Br attacks
Ae KCP__when___,___ Ea,energy barrier is less low temperature
Ae C_=C-H+HCl(HgCl2) to get___only because___ C=C-Cl it is attached to HgCl2 as it has lost its nucleophilicity
Ph-CH(OH)-C_=CH + H+ ->___. Cinnamaldehyde Ph-CH=CH-CH=O
C_=C->(CH2N2 hv)___ C_=C->(CH2N2)___ Cyclopropene 1,2 azacyclopentane
C=C-CN self polymer___. C=C-CN polymer with But-3-yne-1-ene Orlon Buna N
C2H2 +AsCl3,AlCl3___which counteracted by___. Cadet bunsen Lewsite(Cl-C=C-AsCl2) BAL
NCM Ae Rate is proportional to___. Electrophilicity of electrophile Nucleophilicity of nucleophile
NCM Ae Rate in halogens F2>Cl2>Br2>I2
Cis on anti addition gives___. Threo
NCM Ae In HOBr reaction the nucleophile is___. H2O
NOCl___ NCM Ae Cyclic ion opens from that end which is___. Tilden reagent Gives more stable carbocation
Br2 on Anthracene gives___.Cyclic compound which reacts with Br2 9-10 product cylopropane
1,3,5Cycloctatriene with Br2 gives___. Trans 7,8 dibromo Bicyclo[4,2,0]octane.
1,5Cyclooctadiene + Br2 gives 2,6 dibromo bicyclo[3,3,0]octane
>= + X2 at 25 C gives__. Major product by Sae Cl>=
Diels Alder reaction follow cyclic transition state mechanism,concerted mechanism,pericyclic. Rate is proportional to___. EDG in diene EWG in dienophile 1/stearic hindrance
Out of Furan pyrrole thiophene which is not giving Diels alder? Pyrrole thiophene
HCl+ Na___NaNH2___RONa___NaOH___NaHCO3___. Y Y Y Y Y
RCOOH+ Na___NaNH2___RONa___NaOH___NaHCO3___. Y Y Y Y Y
PhOH+ Na___NaNH2___RONa___NaOH___NaHCO3___. Y Y Y Y N
ROH+ Na___NaNH2___RONa___NaOH___NaHCO3___. Y Y Y N N
C_=C ->(Na) only in NH3 there is good yield Other protic solvents can't be used for they are more acidic than terminal alkene
C-C-C_=C+NaNH2->___ AgNO3 NH4OH Cu2Cl2 NH4OH C-C-C_=C(-) Na+ C-C-C_=C(-) Ag+ dirty white C-C-C_=C(-) Cu+ red ppt
C_=C->(__)-(Me-CO-Me)-H2O-ConcH2SO4->H2 Pd Benedicts reagent Isoprene
Terminal alkyne+ NaNH2__ KOH___. Yes No
2-alkyne+ NaNH2__ KOH___. No Yes
2alkyne NaNH2 heat___ Terminal alkyne 1-C- 2-resonance 3-
C_=C+Cu2Cl2 NH4Cl heat___. Vinyl addition
3C2H2(Fe Red hot tube)___. Benzene
4C2H2(Ni(CN)4)___. COT
RC_=C-H+ NaOCl___ +I2 liqNH3 0 C RC_=C-Cl RC_=C-I
CaC2+H2O___ Mg2C3+H2O___ Al4C3+H2O___ Acytelene Propyne Methane
Generation of Grignard reagent R-X + (Et2O Mg) R-Mg-X
Reactivity,nucleophilicity,basicity in decreasing order of organometallic reagents RNa(Wurtz) RMgX(Grignard) R2Zn(Frankland) R2CuLi(Coreyhouse)
Characteristic reactions of carbanion___. Reactions as a base Reactions as a nucleophile nucleophilic addition nucleophilic addition elimination
Strong bases as___and attacks irreversibly to give___.Eg___. Weak bases as___and attack reversibly to give___.Eg___. Hard nucleophile KCP 12 product RNa RLi NaBH4 LiAlH4 soft nucleophile TCP H2S R2CuLi NH2NH2 R2Zn
Monochlorides possible Isobutane 2 2
Monochlorides possible Isopentane Neopentane 6 4 1 1
Monochlorides possible Hexane 3 methylpentane 5 3 8 5
Monochlorides possible Methyl cyclohexane 12 8
Monochlorides possible 2Methoxy propane 3Ethoxy pentane 4 3 10 6
Dichlorides possible Propane Butane Isobutane 5 2 2 1 10 2 5 3 3 1 1 1
Dichlorides possible pentane isopentane neopentane 17 3 6 8 18 4 6 8 2 1 0 1
Dichlorides possible Hexane 26 3 9 14
Chloroderivatives possible Methane ethane propane 4 9 35
Decreasing rate in substrate of Grignard reagent RCOCl RCHO RCOR RCOOR RCONR2 RCOO-
Bu-Cl+Mg Et2O___ Bu-Cl+Na Et2O___ Bu-Cl+.5 Mg Et2O___ Bu-Mg-Cl Bu-Bu Bu-Bu
1,4 dichlorobutane+ Mg Et2O___. 1,4 dichlorobutane+ Mg(excess) COCl2___. Cyclobutane Cyclopentanone
Grignard reagent + acidic H compound___ Grignard reagent + acidic H-lone pair(NH2Cl RONH2)___ RH R-acidic H part 1-RH
RCOOR + H3O+___ RCOOH addition of H+,then H2O,-ROH,-H2O
Soda lime + RCOOH->___.Mechanism___. RH Acid base reaction then Cao+CO2->CaCO3+RH
Rate of oakwood degradation is___. Proportional to stability of carbanion
RCOO-+ MnO/CaO/BaO ->___. Ph-CHBr-C(COOH)-Br heat___ R- Ph-C=C-Br
Compounds like Beta-Keto,Beta-amino acids,Gem dicarboxylic acid,beta-gamma unsaturated acid___. Lose CO2 only on heating
Heating effect beta dioc__ Gamma dioc___ delta dioc___ epsilon and one more dioc___ CO2 eliminated to 1 carbon less carboxylic acid H2O eliminated to cyclic anhydride H2O eliminated to cyclic anhydride CO2 H2O eliminated to cyclopentanone CO2 H2O eliminated to cyclohexanone
2MeCOOH+Conc H2SO4 heat___ 2MeCOOH+CaO/MnO/BaO heat___. Anhydride Acetone
RCOOH->(Ca(OH)2)___->(heat)___. (RCOO)2Ca RCOR
COOH-C-C(OH COOH)-C-COOH->(heat)___. C=C(COOH)-C
Alpha hydroxy carboxylic___ Beta hydroxy carboxylic___ Gamma hydroxy carboxylic___ Delta hydroxy carboxylic___ more longer polymerise on heating. Lactide Cyclic(C-O-C(=O)-C-O-C(=O)) -C=C-COOH Gamma lactone cyclic(C-C-C-O-C(=O)) Delta lactone cyclic(C-C-C-C-O-C(=O))
ALDOL Cyclopropanone___ Bicyclo[2,2,1]octane-8-one___ Me2CH-CH=O___. No aldol No self aldol No self aldol
14 carbon-NO2 Moth repellant
C-CO-C+(NaNO2 HCl)___. C-CO-C=N-OH First tautomerise then attack NO+ then tautomerise
C-CO-C +Br2(excess) Acidic medium___. C-CO-C +Br2(excess) basic medium___. Tautomerise attack of Br2 -HBr Carbanion attack of Br2
C-CO-C +Br2 basic(excess) medium___. C-C-COONa 1st C-CO-C-Br then cyclopropanone then OH- attack then acid base Faversky reaction
C-CO-C +Br2(excess) basic(excess) medium___. CHX3 + C-COO-Na+
Ph-CH(OH)-Me->(CaOCl2 H2O) Do first oxidation
Me-C-NO2+NaNO2 HCl___. Me2-C-NO2+NaNO2 HCl___. Me3-C-NO3+NaNO2 HCl___. C-C(=N-OH)-NO2 Red Me2-C(-N=O)-NO2 Blue White
Me3-C-C(=O)-Me___not formed and fluoroform are formed I Br Cl form not formed
Acetyl acetone ->(iodoform reaction)___. 1 CHI3
Lactic acid Me-C(OH)-COOH
Victor meyer test___. RCOH->(Red P I2)->R-C-I->(AgNO2)R-C-NO2
Mennich reaction Me-CO-Me+HCHO+R-NH2->___by___. Me-CO-C-C-NH-R 1st tautomerise then form carbanion from HCHO then attack
Darzen reaction___. ROH+SOCl2->RCl+HCl+SO2
+I decreasing order CH2->NH->O->COO->CMe3>CHMe2>CH2Me>Me>H
+I decreasing order between isotopes of hydrogen T>D>H
-I decreasing order NF3+>NMe3+>NO2->CN->CHO>COOH>F>Cl>Br>I
-I decreasing order between F,OH,NH2 F>OH>NH2
Basic strength is directly proportional___. EDG 1/EWG steric hindrance
On moving left to right in period or up to down in a group___. Basicity decreases
EtNH2 Et2NH Et3N basicity GP 1<2<3 SP 1<3<2
CH bond energy Proportional to 1/stability of F.R.
+M effect decreasing order CH2->NH->O->OR>OH>OPh NH2>OH>F F>Cl>Br>I OR>SR
-M effect decreasing order Ch2>BH2>PH2 NO2>CN>CHO>COR>COOR>CONH2>COO-
-N=O___SO2H +M as well as -M
Hyperconjugation between H,D,T H>D>T
Order of H M I effects M>H>I
CF3+ CCl+ ion stability order CF3- CCl- ion stability order I>IIp orbital resonance II>Id orbital resonance
C-C(-)-NMe3+ C-C(-)-PMe3+ stability order I>II
The more delocalised are the electrons___. The less basic it is
SIR operates only on bigger groups like___. NO2 SO3H COOH NR2
When group is ortho to basic site in benzene then__. SIP acts
1,8diethylamine naphthalene H protonates then H bond
Stability of butenes >= > TransC-C=C-C > CisC-C=C-C > C=C-C-C
Vitamin C CH2OH-C(OH)-cyclic(C-O-C(=O)-C(OH)=C(OH))
Acidic order of common organic acids HCl>RCOOH>H2CO3>PhOH>H2O>ROH>RC_=CH>NH3>RC=C>CH3
CHCl3 CHF3 acidity order I>II
PhOH squaric acid acidic order Squaric acid
Ortho meta para halophenol acid order Meta>para>ortho
Ortho meta para Ph-F,Ph-Cl,Ph-Br,Ph-I acidic order Cl>Br>F>I
COOH-Ph-SO3H COOH-Ph-NO2 acidic order COOH acidic order II>I Total acidic order I>II
Four groups of electrophiles + incomplete octet 0 incomplete octet 0 expanded octet o complete not expanded H+ R+ X+ NO2+ NO+ Me-CO BH3>BX3 BF3<BCl3 free radicals PCl3 FeCl3 ZnCl2 SbCL3 XX RX CO2 SO3 CCl4
Groups of nucleophile - charged neutral LP pi electron
On going left to right in a period___. Nucleiphilicity basicity decreases
On going up to down in a group___. Nucleophilicity increases in polar protic solvent Nucleophilicity decreases in polar aprotic solvent
Polar aprotic solvents DMF HMPT DMA DMSO crown ether
Nucleophilicity order SH->P(CH3)3>CN->I->OCH3->OH->Br->Cl->NH3>OAc-
Lg tendency order NH3+>I->H2O+=Br->Cl->>F-
Carbocation stability 3>2>allylic>benzylic>1
___solvents increase the rate of E2 reaction. Polar aprotic
Increasing rate for E2 reaction 3>2>1 strong bases
A reaction is___when it yields predominantly or exclusively one constitutional isomer when more than one is possible. Regioselective
A reaction is___when it forms predominantly or exclusively one stereoisomer when two or more are possible. Stereoselective
The E1 and E2 mechanisms both involve the same number of bonds broken and formed. The only difference is___. Timing
E1 CHARACTERISTICS 1st order 2steps 3>2>1 weak base good lg polar protic solvent
For E2 elimination, the C-Cl bond must be anti periplanar to the C—H bond on a β carbon, and this occurs only when the H and Cl atoms are both in the axial position. The requirement for__means that elimination must occur. Trans diaxial geometry
___favor E2 mechanism. ___favor E1 mechanism. Strong bases,order of reactivity weaker bases,1 C carbocations
With strong bases and 3 C carbon___. E2 mechanism
With weak nucleophiles or bases and 3 C Carbon Sn1 and E1 mechanism
With 1 C Carbon and strong nucleophiles Sn2
With 1 C Carbon and strong sterically hindered bases E2 mechanism
With 2 C Carbon and strong bases and nucleophiles Sn2 E2 mechanism
With 2 C Carbon and strong sterically hindered bases E2 mechanism
With 2 C Carbon and with weak nucleophiles or bases Sn1 and E1 mechanism
Methyl 1 C Carbon Weak base/poor Nu,poor base/good Nu,strong base/good Nu,strong base/poor Nu NR Sn2 Sn2 Sn2 NR Sn2 Sn2 E2
2 C Carbon Weak base/poor Nu,poor base/good Nu,strong base/good Nu,strong base/poor Nu Sn1,E1 Sn2 Sn2,E2 E2
3 C Carbon Weak base/poor Nu,poor base/good Nu,strong base/good Nu,strong base/poor Nu Sn1,E1 Sn1,E1 E2 E2
1 C Benzylic 2 C Benzylic 3 C Benzylic Weak base/poor Nu,poor base/good Nu,strong base/good Nu,strong base/poor Nu Sn1 Sn2 Sn2 Sn2 Sn1,E1 Sn2 Sn2,E2 E2 Sn1,E1 Sn1,E1 E2 E2
1 C allylic 2 C allylic 3 C allylic Weak base/poor Nu,poor base/good Nu,strong base/good Nu,strong base/poor Nu Sn1 Sn2 Sn2 Sn2 Sn1,E1 Sn2 Sn2,E2 E2 Sn1,E1 Sn1,E1 E2 E2
What is an oxidative addition? A neutral ligand adds to a metal center and oxidizes the metal and oxidizes the metal at least one anionic ligand becomes attached to metal center
Non-electrophillic case example H-H S-S C-H C-C
Electrophilic case example X2 R-X Ar-X H-X O2
Reductive elimination Two cisoidal anionic ligands on a metal center couple together
Migratory insertion Cisoidal anionic and neutral ligand on a metal complex couple together
In migratory insertion what is not changed? Oxidation state or d electron-count but the overall electron-count on metal decreases by 2e-
Which anions and neutral molecules can perform migratory insertion? H- R- Ar- acyl- O2- CO alkenes alkynes carbenes
A migration is when the___and performs a nucleophillic-like intramolecular attack on the electrophillic neutral ligand. An insertion is when the neutral ligand moves and___. Anionic ligand moves "inserts” into the bond between the metal and anionic ligand
Fe(C5H5)EtPPH3CO->(CH3NO2)____. (HMPA)___. Et migrates CO inserts
Alkene manafacturing by Zr(C5H5)2CH3 involves____. Migratory insertion
An alkene and a hydride usually react via a___to the coordinated alkene ligand Migration of the hydride
RNH2->(NaNO2 HCl)___(CAN)___. R2NH->(NaNO2 HCl)___ R3N->(NaNO2 HCl)___ ROH red R2N-N=O oily liquid No effect
Ph-NH2(NaNO2 HCl)___(alkaline beta napthol) Ph-NHR(NaNO2 HCl)___ Ph-N2+Cl- Red Ph-N(-N=O)-R oily liquid
ROH+Lucas reagent(ZnCl2+HCl)->___ alcohol turbidity time 3 degree___2 degree
ROR(HI anhydrous)->___ ROR(Conc HI)->___. ROR(dilute HI)->___. Sn2 Sn1 Sn1
R-X+NH3 which type reaction where R-1 degree___ R-3 degree___ Sn2 elimination
NCH3 NPh3 PCH3 PPh3 which does not react with MeI___. NPh3
R1-O-R2 (dil H2SO4)->___. Follow Sn1 reaction
Me-NH-Et(anhydrous HI)___ "(anhydrous HI)___ "(conc HI)___ (MeNH2Et)+I- Me-I EtNH2 Me-I EtNH2 Hurzig mayer method
OH-C-C-OH(HCl+ZnCl2)->____. Cl-C-C-Cl No adjacent carbocation
R-I+NaI(acetone)->___. R-I Finkelstein reaction
R-Cl+KF(DMF)->___. R-F Swarts reaction
MeCl+RONa->___. ROMe williamson synthesis
Me-Cl+(KCN,AgCN,AgCN(DMF))->___. Me-Cl+(KNO2,AgNO2)->___. Me-CN Me-NC Me-CN MeONO MeNO2
R-C_=N->(H2O H+)___ R-C_=N->(H2O OH-)___ RCOOH NH4+ RCOO- NH3
RCN+H2___. R-C_=N(Sn+HCl)___. RCN(stephen reagent)->___. RCH=NH RCH2-NH2 RC=NH
MeCl+ alc AgNO3->___ MeCl+ aqAgNO3->___ Me-ONO2 NO3- is more solvated
Me3C-Cl+(alcAgNO3,aqAgNO3)->___,___ Me3ONO2 AgCl major Me3COR Me3COH major
For anchimeric assistance conditions are___. Internal Nu,anti,concentration of external Nu must be low
Me3N+OH- ->___ Me3S+OH- ->___ Me3S+I- ->___ NMe4+I- -> Sn2 Sn2 Sn1 Sn2
Me-C-(OMe)3___. Methyl orthoacetate
All halogen compounds burn with green edge flame___. Belstein test
ROH+RedP/I2___. P(ROH)3->RI Sn2 mechanism
ROH+Red P/HI->___. RH+H3PO3
In propagation step the polymer chain growth happens from___. Migratory insertion
Sum(niMi)/sum(ni) Sum(niMi^2)/sum(niMi) Mw(avg)/Mn(avg) Mn(avg)=___Mw(avg)=____PDI=___.
What is the basis of M(w)? More weighty molecules contribute more to the properties of the polymer
As the distribution narrows the dispersivity approaches___. 1
What factor most effect stereochemistry if the polymerization? Steric environment around the metal corner
C2 symmetry(chiral) produces___environment. Bulky small catalyst environment produces___. Small ligands that offer little steric directing effect produce___. Isotactic syndiotactic atactic
SBR rubber is made from Styrene butadiene
Metathesis refers to the reaction of two unsaturated substances that leads to a___. Switching of the atom groups on each end of the bond with unsaturation
Which reaction is used to produce 11-tetradecenyl acetate which is used in orange protection? 3-Hexene+Eicosenyl acetate Metathesis
LnM-Cl+AlR3/MAO/ZnR2->___. LnM-R+AlR2Cl Initiation
Polymerization propagates through___. Migratory insertion
M-CH3+C2H2->___->(___)->so on. M(C2H2)-CH3 M-CH2-CH2-CH3
Olefin metathesis constitutes a catalytic methods for both___C=C double bonds.The reaction is generally___. Cleaving and forming reversible
Chauvin mechanism for metathesis___. R-C=CH2->(R-C=[M])R-C(-M-CH2-)C-R->(R=Rout)M=CH2->(R-C=CH2)R-CH(-M-CH2-)-CH2
In 1995 Grubbs reported the synthesis of RuCl2(=CHPh)(PCy3)2 in high yield and purity.This complex is obtained as a___.It is very famous for ease synthesis,high catalytic activity,it constitute the___. Purple microcrystallne The most useful catalysts
Homogeneous catalysis are good because___. More selective,more active,more easily studied,easily modified for optimizing selectivity
Homogeneous catalysis are bad because___. Senstitive to permanent deactivation,difficulty in separation
Exposure to elemental Hg will___whereas exposure to polythiols will___. Poison heterogeneous catalyst poison homogeneous catalyst
One loop through the catalyst cycle.Typically one equivalent of reactant is converted to one equivalent of product(per equivalent of catalyst) Turnover
The absolute number of passes through the catalytic cycle before the catalyst become deactivated. Turnover number
The number of passes through the catalytic cycle per unit time Turnover frequency=n(products)/(n(catalysts)t)
Hydrogenation process step1 three methods___. Oxidative addition LnM+H2<=>LnM(H,H) hydrogenolysis LnM-X+H2<=>LnM-X+HX heterolytic cleavage LnM+H2+B-<=>[LnM-H]-
Hb MW=___,alpha___,beta___,active site___. 64,500 g 141 146 Fe A tetramer of hemoglobin
Mb MW=___,alpha___,active site___. 17,800 g 161 Fe
Reaction of Fe with O2___. Fe(II)+O(2)->Fe(II)-O(2) Fe(II)-O2+Fe(II)->peroxocomplex(III) Fe(III)-O-O-Fe(III)->2Fe(IV)=O Fe(IV)=O+Fe(II)->oxo complex Fe
Coordination environment of Fe(II)in deoxymyoglobin and oxymyoglobin___. (Poryphyrin)Fe-Proximal His-F helix on another side-distal His-E helix
Fe(N(poryphyrin))4N(His) Fe(N(poryphyrin))4N(His)O2- x2-y2(|) z2(|) xy(|) xz(||)yz(||) xy(||) xz(|)yz(|)
Role of distal base in hemoglobin Sterically weaken CO bond
S shaped hyperbolic Hemoglobin(percent O2 vs partial pressure of O2)___,Myoglobin___.
The role of Myoglobin is to store___. Store the oxygen and release it for metabolic
Why Fe doesnt' forms oxo complex with oxygen with in hemoglobin? Because of steric hindrance of proteins
The coordination environment comprises of four nitrogens from the porphyrin ring, one___arising out of the amino acid residue, histidine, of the protein chain, and possibly a second distant imidazole nitrogen or a water molecule. Imidazole nitrogen
Fe is___above the poryphyrin plane. .4 A*
___and___are nonheme comoounds in which the metal is bound directly to the protein Hemerythrin hemocyanic
Hemerythrin is found in___.Hemocyanin,a copper protein is found in___. Marine animals mollusks and arthopods
Aquatic mammals are particularly rich in myoglobin;the concentration in some cases is so high that skeletal muscles appear___. Almost black in color
Monomeric hemoglobins also occur in blood of___and___. Invertebrates roots of legumes
These high molecular weight hemoglobins, which may contain up to 200 hemes per molecule. are also called___. Erthrocruorins
Which in exception of all vertebrates have hemoglobin? Ice fish
Invertebrates don't seem to follow___.Sea ccumber Molpadia arenicola bleeds profusely but___doesn't contain. Any evolutionary scheme Close relative starfish
Hemerythrins___/Fe MW___. Hemocyanins___/Cu MW___. 7000 40000-108000 Mollusk=25000 4-9x10^6 Arthopod=37000 .5-3x10^6
Myoglobins___/Fe MW___. Legheglobbins___/Fe MW___. Invertebrate hemo___/Fe MW___. Vertebrate hemo___/Fe MW___. Chlorocruorins___/Fe MW___. 18000 18000 16000 16000 16000-40000 16000-6x10^6 16000 65000 22000-35000 3x10^6
Four of the six coordination spaces around the metal are occupied hv the nitrogens of the poryphyrin.In the fifth space is the___of a histidine residue,the 8th amino acid of the helical region laheled F Four Imidazole nitrogen
In O2-free hemoglobin the iron is in the___and has a high spin configuration +2 oxidation state
Created by: jatint