lecture 8

Question 1

what are the 2 types of bonding in cyclophosphazines

Answer 1

theres in plane pi bonding (N: is in the sp2 hybrid and it donates into the next PN sigma*)

out of plane pi bonding:
( N: is in the pz orbital and is donated into the PX sigma* where X is the substituent on P,, if this is EWG,, its preferred as this lowers the energy of the sigma* orbital) also not truley aromatic

makes PN bonds very strong,, so reactivity is low,, theres a ring retention (no cleavage)

Question 2

why isnt cyclophosphazine that reactive

Answer 2

its not aromatic bc theres not complete delocalisstion of e-.

due to there being 2 types of pi bonding,, the PN bonds are very strong,, meaning theres ring retention as it doesnt want to cleave.

the N: is also involved in P back bonding and therefore isnt rlly used to react with stuff,, no reaction at N

most reactions are at P!!

Question 3

N: areeee,,,, and why

Answer 3

theyre weakly basic

aka they are weakly donated

bc theyre backbonded to P

Question 4

can N: still react even tho theyrinvolved in backbonding to P

Answer 4

yesss!!

but usually only with strong lewis acids or bronzed acids!!!

H+ or HCl H2SO4

or strong electrophile SO3

Question 5

the N: in cyclophosphazines with Cl on the P is weakly basic,, what do we use to react with it

Answer 5

we use SO3 - a very strong acceptor
u get an SO3 bonded at every N

can use H+ with HCl
u get a H on 1 nitrogen only!! unless u add more H+.

Question 6

the ability of the N: to react,, depends on whatttttt

Answer 6

it depends on the R group on P

bc N: in plane back donation

back donation depends on how delta (+) the P is

EWG on P = P more positive = more back donation of N: –> P

Question 7

more EWG on P in cyclophosphazines

Answer 7

more EWG = P is more + (CF3)

means the N: is more likely to back donate in in plane pi bonding into the PN sigma*

N: is less basiccc + less reactive

Question 8

more EDG on P in cyclophosphazines

Answer 8

P is less + and more - (amine // alkyl group)

less in plane pi bonding back donation of N: to NP sigma*

N: are less basic + more reactive.

Question 9

most reactivity in cyclophosphazes occurs where

Answer 9

at the P

normally substitution reactions on halides on the P.

Question 10

P SUBSTITUTION ON CYCLOPHOSPHAZINES IS SIMILAR TO WHAT REACTION

Answer 10

sn2 reaction

one step

switch the halide for the nucleophile

Question 11

cyclophosphazine with Cl and excess nucleophile (KF)

Answer 11

F- as nuc

each Cl is substituted for F.

-F attacks the P!! and kicks off the other halide// substituent.

all the halides –> F

+ 6KCl

Question 12

cyclophosphazines with Cl and amines (12NH3)

Answer 12

each Cl is substituted for an aminne ligand so NH2 is attached

so u get 6HCl as the product!!

HCl (an acid) reacts with base (NH3) to form a salt

6HCl reacts with NH3 to form 6NH4Cl!! acid is mopped up by the base

so if u see 12NH3,, u only add 6 to the ring!!!

if u see 4NH3 u add 2 to the ring,, bc the rest mops up each HCl formed to give 2NH4Cl (ammonium chloride salt)

Question 13

cyclophsophazine with Cl reacting with excess azides (sodium azides)

Answer 13

substitute each Cl for an azide (N3)

each Cl–> N3

explosive.

lots of N atoms = explosive.

Question 14

cyclophosphazines with Cl withhh limited nucleophiles: do they attack the same P or nope:

Answer 14

1st nuc attacks any P bc theyre all idensiical if theyre all bonded to Cl.

so now 1 is bonded to the nuc.

2nd nuc goes to the same P: geminal product!!

2nd nuc goes to other P: non geminal product!!

Question 15

whats special about non geminal substitution

Answer 15

the P is sp3 hybridised,, meaning theres stereochemistry

the nuc can either go on the dashed or wedged lines

so u can get isomers!!

both dashed = cis
both wedged = cis
one wedge one dash = cis

Question 16

bulky ligands when substituted on cyclophosphazine in a nongeminal way

Answer 16

they before being far away and therefore being transsss

Question 17

what determines if the nuc attacks the same P or different,, when nuc attacks cyclophosphazine.

Answer 17

• if nuc bonded activated the P: we add the second nuc at the same P GEMINAL (F-, RO- ,, hard electronegative ligands)
• if nuc bonded deactivates the P,, we add the second nuc on a different P

Question 18

hard nucleophiles

Answer 18

small
high charge

Question 19

soft nucs

Answer 19

large
easily polarisable

Question 20

cyclophosphazines with hard nucs + soft nucss giveee

Answer 20

geminal products

same P due to it being activated

Question 21

what does the P activation on cyclophosphazine when doing nucleophilic substitution depend on

Answer 21

electrostatic : hard nucs (F,O)
polarisation: soft nucleophiles (RS-)

Question 22

polarisation reasons contributing to site activation on P when doing nucleophilic substitution.

Answer 22

look at the transition state: SN2 type transition state,, where Lg and incoming nuc comes in at the opposite side.

P dashed with Nuc and LG to show bonds forming and breaking.
we need to rehybridise + reorganise orbitals in the TS and this is easier when we have polarisable ligands. also S is more similar and energy and size with P. they lower the energy barrier of the reaction!!

soft ligands lower the EA of the reaction from SM –> products. the reaction is more favourable. due to easier rehybridisation of the TS. gives geminal substitution

Question 22

electrostatic reasons contributing to site activation on Pwhen doing nucleophilic substitution

Answer 22

when incoming nuc is more electronegative than the LG // old X substituent on P.

when u add an F,, the P becomes more deltaP than the other P’s (with the old X substituent)
so the next nuc attacks it as its more + and reactive.

gives geminal product

Question 23

whats needed for geminal subs

Answer 23

highly electronegative nucs (F,RO-)

softer and more polarisable nucssss (sulfur)

Question 24

when does non geminal substitution occur

Answer 24

when incoming nuc is less electronegative than the previous substituent on P.

P will have more electrondensity than the other ones so the nucs wouldnt be attracted to that one anymore, theyll attack a different P.

also if the nuc isnt soft enough enough to allow reorganisation and rehybridisation of nucleophiles.

Question 25

what nucleophile DEACTIVATES P

Answer 25

nitrogen nucleophiles!!

ammonia NH3
amines RNH2

bc they have a lone paie that donates to the P and deactivates it. it increases e- density at P so nucs wont be attracted to it anymore. bc its deactivated.

remember that when u have the Cl cyclophosphazine and N nuc,, u only add 1/2 of them as the other nucs react with the HCl to give a salt!!! ammonium chloride salt

the NH2 go at different P’s - nongeminal

Question 25

what do we need to rmemeber when using N nucs

Answer 25

remmeber that u only add half of them to the cyclophosphazine!!!

the other half will mop up the HCl to give ammonium salts!!

also remember that N donates its lone pair to the P which deactivates it,, so u get nongeminal products. aka different N nucs will attack different P’s.

Question 26

non geminal isss

Answer 26

when nucs attack different P’s

u can get isomers depending on if theyre both dashed// wedged to give cis.. or opposites to get trans

Question 27

geminal isss

Answer 27

when nucs attack the same P

think geminal where thr C had 2 OH’s

du to activation of P,, due to hard // soft nucs due to electrostatic // polarisation strategies which make the P more attractive to NUCs.

either by removing electron density and making it more +

or by lowering the Ea of the reaction making it more favourable due to making the rehybridisation // reorganisation of orbitals easier.
if the P is sp3 hybridised

X —- P —— NUC (breaking and making bonds)

Question 28

when amines are the nucs to the cyclophosphazine with the Cl’s how should we add them to be most stable

Answer 28

try to get 2 cis and 1 trans.

aka 2 wedged and 1 dashed sp theyre not all cis to one another

Question 29

what hybridisation is seen in RRN ligand

Answer 29

sp2 pi donor

lone pair in the P orbital

donates to the cyclophosphazine P (either the d orbital or the sigma* of the PN ring - backdonation of N” into one of the PN sigma* orbitals )

remember u only use halfffffff of the number of nucs.,, the rest mop up the HCl to give ammonium chloride salts and the nongeminal product!.

u get trans for less steric hinderance.

think about which one is chiral!! think about flipping it and seeing if the things are the same or not - redo that organic workshop we love

Question 30

what can we use to see if smt is geminal or not geminal

Answer 30

we can use P NMR to see if we will get geminal or nongeminal substitution!!

Question 31

spin of P

Answer 31

i = 1/2

Question 32

is Cl nmr active

Answer 32

nopee so we dont see in P nmr

Question 33

spin of F

Answer 33

i = 1/2

Question 34

the cyclophosphazine where u have the Cl’s attached is calleddd

Answer 34

chlorophosphazine!!

Question 35

geminal substitution of 2F on chlorophosphazine what is seen in P nmr

Answer 35

• look at P bc P NMr
• 2 diff P environments
• assume no coupling through the ring (no coupling to P)
• singlet for PCl2
• triplet for PF2

Question 36

chlorophosphazine boned to 2F,, what will we see in F NMr

Answer 36

• look at F bc F nmr
• F = 1 env
• coupled to 1P
• so doublet

Question 37

can cyclophosphazines with the Cl: chlorophosphazines readily react with 6water

Answer 37

yesss

-6HCl
and u put an OH at every P where there was F,,

6 OH’s in the new molecule

this tautomerises: H moves from P to N,, N: attacks H,, OH e- form double bond from P to O,, P=N breaks to give P-N.

the cycle is now made up of single bonds.
p=o and OH
N-H

this occurs bc the P=O bond is very very strong : so this is the driving force of the reaction.
RING IS NO LONGER PLANAR - MORE OF A CHAIR CONFORMATION!!