There is no such bolt size as 4.5mm, if you look in to an imperial size bolt instead you will find that the imperial size converts back to 4mm or 5mm (M4 or M5 and nothing in the middle).
Samsung can not advise on the correct bolt for your tv model as they do not have the specification for this, this is a factory error - no other Samsung model hase this problem.
You can use PTFE tape, wrap this around the M4 bolt to give it .5mm, PTFE tape is used by plumbers to make screw threads water tight when using compression fittings.You can buy PTFE tape from any DIY store.
I have a samsung LE model, 32", I bought a TV wall bracket from an excellent website called http://www.mountright.com , they supplied with a UMount TV bracket which came with all the correct bolts for my Samsung TV.
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Thank you for your advice - you are confirming what I had read on a few bulletin boards. It does seem an extraordinairy thing for Samsung to do.
In the meantime I have managed to find bolts athttp://www.stagonset.co.uk/ which are something called A2_ScrewBolt_SHCap_UNCoarse8-32_5/8_THRfull. These work out to 4.2mm so they may work, especially with the PTFE tape you metion - I havent tried them yet.
thank you again for your speedy update
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